bluuebunny/crossref_metadata_2025 huggingface dataset:
Technical note: A linear model for predicting δ13Cprotein
Authors: Pestle William J. , Hubbe Mark , Smith Erin K. , Stevenson Joseph M.
Published: March 2015

Objective: Development of a model for the prediction of δ13Cprotein from δ13Ccollagen and Δ13Cap‐co. Model‐generated values could, in turn, serve as “consumer” inputs for multisource mixture modeling of paleodiet. Methods: Linear regression analysis of previously published controlled diet data facilitated the development of a mathematical model for predicting δ13Cprotein (and an experimentally generated error term) from isotopic data routinely generated during the analysis of osseous remains (δ13Cco and Δ13Cap‐co). Results: Regression analysis resulted in a two‐term linear model (δ13Cprotein (%) = (0.78 × δ13Cco) − (0.58× Δ13Cap‐co) − 4.7), possessing a high R‐value of 0.93 (r2 = 0.86, P < 0.01), and experimentally generated error terms of ±1.9% for any predicted individual value of δ13Cprotein. This model was tested using isotopic data from Formative Period individuals from northern Chile's Atacama Desert. Conclusions: The model presented here appears to hold significant potential for the prediction of the carbon isotope signature of dietary protein using only such data as is routinely generated in the course of stable isotope analysis of human osseous remains. These predicted values are ideal for use in multisource mixture modeling of dietary protein source contribution. Am J Phys Anthropol 157:694–703, 2015. © 2015 Wiley Periodicals, Inc.
Quantum bottlenecks and unidirectional energy flow in molecules
Authors: Leitner David M. , Pandey Hari Datt
Published: March 2015

Quantum mechanical effects can enable energy to flow more efficiently in one direction along a molecule than in others. Ultrafast spectroscopic experiments on substituted benzenes [J. Phys. Chem. B 117, 10898 (2013)] reveal such an asymmetry in the flow of vibrational energy between the two chemical groups of the molecule, i.e., between the phenyl and the substituent. We examine theoretically energy flow in toluene, one of the substituted benzenes probed in the recent experiments, and show that quantum mechanical bottlenecks give rise to a preferred direction of energy flow in this molecule.

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Ein Pyren‐fusioniertes N‐Heteroacen mit elf linear anellierten aromatischen Ringen
Authors: Kohl Bernd , Rominger Frank , Mastalerz Michael
Published: March 2015

Ein sehr gut lösliches Pyren‐fusioniertes Undecacen wurde durch Anbringung endständiger Triptycenylen‐Einheiten an das lineare aromatische π‐System realisiert. Neben der guten Löslichkeit zeigt die Verbindung eine hohe Kristallisationsneigung. Zwei Polymorphe aus Dichlorbenzol und Chloroform werden beschrieben. In dem Polymorph aus Chloroform zeigt die Hälfte der Moleküle eine ausgeprägte Krümmung aus der π‐Ebene von 26.4°.
Creep characterization of vapor‐grown carbon nanofiber/vinyl ester nanocomposites using a response surface methodology
Authors: Drake Daniel A. , Sullivan Rani W. , Lacy Thomas E. , Pittman Charles U. , Toghiani Hossein , DuBien Janice L. , Nouranian Sasan , Simsiriwong Jutima
Published: March 2015

The effects of selected factors such as vapor‐grown carbon nanofiber (VGCNF) weight fraction, applied stress, and temperature on the viscoelastic responses (creep strain and creep compliance) of VGCNF/vinyl ester (VE) nanocomposites were studied using a central composite design (CCD). Nanocomposite test articles were fabricated by high‐shear mixing, casting, curing, and post curing in an open‐face mold under a nitrogen environment. Short‐term creep/creep recovery experiments were conducted at prescribed combinations of temperature (23.8–69.2°C), applied stress (30.2–49.8 MPa), and VGCNF weight fraction (0.00–1.00 parts of VGCNF per hundred parts of resin) determined from the CCD. Response surface models (RSMs) for predicting these viscoelastic responses were developed using the least squares method and an analysis of variance procedure. The response surface estimates indicate that increasing the VGCNF weight fraction marginally increases the creep resistance of the VGCNF/VE nanocomposite at low temperatures (i.e., 23.8–46.5°C). However, increasing the VGCNF weight fraction decreased the creep resistance of these nanocomposites for temperatures greater than 50°C. The latter response may be due to a decrease in the nanofiber‐to‐matrix adhesion as the temperature is increased. The RSMs for creep strain and creep compliance revealed the interactions between the VGCNF weight fraction, stress, and temperature on the creep behavior of thermoset polymer nanocomposites. The design of experiments approach is useful in revealing interactions between selected factors, and thus can facilitate the development of more physics‐based models. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42162.
Film blowing of PHBV blends and PHBV‐based multilayers for the production of biodegradable packages
Authors: Cunha Mara , Fernandes Bruno , Covas José A. , Vicente António A. , Hilliou Loïc
Published: March 2015

Poly(hydroxy butyrate‐co‐valerate) (PHBV) is a biodegradable polymer that is difficult to melt process into films. Such difficulty is mirrored in the lack of literature on film blowing of PHBV‐ or PHBV‐based materials. To circumvent this problem, 70/30 wt % blends of PHBV with a biodegradable compound (PBSebT), or with poly(butylene adipate‐co‐terephtalate) (PBAT), were prepared and tested for extrusion film blowing. Both blends showed a similar rheological pattern at 175°C, which is the maximum processing temperature with tolerable thermal degradation. Blending stabilized the film bubbles, thus widening the processing window. However, film properties such as tensile modulus, strain at break and tear resistance remained isotropic and crystallinity characteristics in the machine and transverse directions were generally similar. To bypass the thermal degradation associated with polymer blending, PHBV/PBAT films were coextruded. These showed enhanced functional properties when compared with films blown from blends. The mechanical properties of bilayered films matched those of films blown from commercial PBAT designed for food packaging. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 42165.
Changes in hydrogen bonding in protein plasticized with triethylene glycol
Authors: Hicks Talia Maree , Verbeek Casparus Johannes Reinhard , Lay Mark Christopher , Manley‐Harris Merilyn
Published: March 2015

Bloodmeal decolored with 4 wt % peracetic acid can be extruded into a semi‐transparent bio‐plastic through the addition of sodium dodecyl sulfate (SDS), water, and triethylene glycol (TEG). TEG is often used to plasticize protein thermoplastic materials because of its ability to form both hydrophobic and hydrogen bonds. Synchrotron‐based FT‐IR was used to monitor changes in the types of hydrogen bonding occurring in TEG plasticized protein during heating. Heating was found to overcome a portion of the weaker hydrogen bonds found within and between proteins, observed as a blue‐shift in the N‐H and O‐H stretching vibrations occurring at ∼3280 cm−1. TEG was shown to be involved in a larger array of hydrogen bonding environments after heating, evidenced by the broadening of the C‐OH stretch around 1076 cm−1, suggesting improved plasticizer‐protein interactions. Additionally, these bonds were found to be as strong as the original interactions, observed as a shift in the C‐OH peak back to its original wavenumber (∼1076 cm−1) during cooling. Initially, TEG was spatially distributed into distinct plasticizer‐rich and plasticizer‐poor domains, giving rise to two glass transitions. Heating allowed the migration and uniform dispersion of TEG throughout the material, and merged the two glass transitions into one broader glass transition region. Heating during DSC removed the peak around 60°C corresponding to the enthalpy of relaxation, which is associated with physical aging of amorphous and semi‐crystalline polymers. While physical aging occurred during the storage of DBM, in the presence of TEG it occurred to a lesser extent. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42166.
Polyethylene battery separator with auto‐shutdown ability, thermal stability of 220°C, and hydrophilic surface via solid‐state ultraviolet irradiation
Authors: Gao Xiang , Sheng Wei , Wang Yongchang , Lin Yegang , Luo Yingwu , Li Bo‐Geng
Published: March 2015

To assure the safety of the lithium‐ion battery, the separator is required to have good thermal stability. Because the single‐layer polyethylene (PE) separator can only tolerate a temperature of 130°C, it is seldom employed currently by lithium‐ion battery manufacturers although its cost is low. In this article, we modified PE separator chain structure through solid‐state ultraviolet (UV) irradiation method to achieve a separator with composite structure of ∼40% crystallized PE and ∼70% gel content. Approximately 40% crystallized PE chains fulfill the task of auto‐shutdown at 130°C through melting and filling the pores. At the same time, the PE separator can maintain integrity till 220°C because of its highly cross‐linked chain structure. Besides, the modified PE separator is hydrophilic with a water contact angle of 33° after UV treatment and is able to absorb more electrolyte. However, the tensile strength and elongation at the break decreased because the cross‐linking network increased the rigidity. Nevertheless, these values still meet the requirements as the separator for lithium‐ion battery. Considering the low cost and easy preparation, current cross‐linked PE separator has potential to be used in lithium‐ion batteries for various applications, including electric vehicles and energy storage purpose. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42169.
Significance of polymer on emulsion stability in surfactant‐polymer flooding
Authors: Xuan Yinglong , Ma Desheng , Zhou Minghui , Gao Ming
Published: March 2015

The influence of polymer on stability and shear rate on droplet size of emulsion is evaluated in the laboratory, microstructure of the emulsion is observed under a microscope, and the pore distribution of the cores is analyzed through mercury injection experiments. In the process of surfactant‐polymer (SP) flooding, the thickness of polymer absorbed on the surface of the rock is calculated by a mathematical model. The experiments show that the polymer is good for the stability of emulsion, with the increase of shear rate, stability becomes better, and droplet size gets smaller. Due to the adsorption of polymer, the pore throat turns narrow, seepage velocity is increasing, and also the emulsion becomes more stable with the smaller‐size droplets. During the single emulsifier flooding, the emulsion is easy to coalescence for its instability, and the seepage channel can be easily blocked, which leads to the high injection pressure. Consequently, the polymer plays an important role on emulsion stability in SP flooding. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42171.
Depolymerization of renewable resources—lignin by sodium hydroxide as a catalyst and its applications to epoxy resin
Authors: Chen Hong‐Zhuo , Li Zhi‐Ying , Liu Xin‐Yu , Tian Yu‐Mei , Yang Liu , Wang Zi‐Chen
Published: March 2015

Alkali lignin was successfully depolymerized into polyols with high hydroxyl number via direct hydrolysis using sodium hydroxide (NaOH) as a catalyst, without any organic solvent agent. Hydrolysis of lignin can produce a multitude of high‐value products via alkali‐catalyzed cleavage. This process usually gives good results with respect to the yield of phenols. Through this method, the numbers of the hydroxymethyl and phenolic hydroxyl groups of lignin had been dramatically increased, reaching 2.11%, nearly four times higher than that in the original one. Meanwhile, we added the same amounts (20 wt %) of different depolymerization of lignin (DL) into epoxy resin (EP), and the results showed that DL could not only increase the decomposition temperature of EP, but also remarkably improve its mechanical properties. The optimum reaction time was 1.5 h, the reaction temperature was 250°C, and the optimum sodium hydroxide concentration was 15 wt % for depolymerizing lignin. The mechanical and thermal properties of cured lignin‐based epoxy resin (LEP) were compared with cured neat EP. The cured DL‐based epoxy resin (DLEP) showed the highest adhesive shear strength up to 2.66 MPa, which displayed 122% of the adhesive shear strength of EP. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42176.
Fabrication of pH‐sensitive poly(2‐(diethylamino)ethyl methacrylate)/palygorskite composite microspheres via Pickering emulsion polymerization and their release behavior
Authors: Lu Jia , Wu Jie , Chen Jing , Jin Yeling , Hu Tao , Walters Keisha B. , Ding Shijie
Published: March 2015

The poly(2‐(diethylamino)ethyl methacrylate)/palygorskite (PDEAEMA/PAL) composite microspheres were prepared via Pickering emulsion polymerization using palygorskite (PAL) as an emulsifier. The morphology, chemical structure, and content of PDEAEMA/PAL composite microspheres were investigated by polarizing optical microscopy, scanning electron microscopy (SEM), Fourier‐transform infrared (FT‐IR) spectroscopy, and thermal gravimetric analysis (TGA). The pH‐responsive behavior of composite microspheres was studied by measuring their size at different pH values. Furthermore, their release behavior was investigated using rhodamine B (RhB) as a model molecule. It was proven that the release properties of RhB from PDEAEMA/PAL composite microspheres could be controlled by adjusting the pH values. The study of release kinetics found that Higuchi model was fit for RhB release from PDEAEMA/PAL composite microspheres at pH 5.0, 7.4, and 10.0. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42179.
THE EFFECTS OF XANTHOTOXIN ON THE BIOLOGY AND BIOCHEMISTRY OF Galleria mellonella L. (LEPIDOPTERA: PYRALIDAE)
Authors: Erdem Meltem , Büyükgüzel Ender
Published: March 2015

The effects of a dietary plant allelochemical, xanthotoxin (XA), on survivorship, development, male and female adult longevity, fecundity, and hatchability of the greater wax moth Galleria mellonella L. were investigated. Oxidative stress indicators, the lipid peroxidation product, malondialdehyde (MDA), and protein oxidation products, protein carbonyl (PCO) contents, and activities of a detoxification enzyme glutathione S‐transferase (GST) activity were determined in wax moth adults. The insect was reared from first‐instar larvae on an artificial diets containing XA at 0.001, 0.005, or 0.1% to adult stage in laboratory conditions. Relative to the controls, the diets containing XA concentrations led to decreased survivorship in seventh instar, pupal, and adult stages. Compared to control diet (77.7%), the highest dietary XA concentration decreased survivorship to adulthood to 11.0%. The highest XA concentration (0.1%) reduced female longevity from 10.4 to 5.7 days and decreased egg numbers from 95.0 to 33.5 and hatchability from 82.7 to 35.6%. The lowest XA concentration (0.001%) led to about a sixfold increase in MDA content. XA at high concentrations (0.005 and 0.1%) increased MDA (by threefold) and protein carbonyl (by twofold) contents decreased GST activity. The highest dietary XA concentration decreased GST activity from 0.28 ± 0.025 to 0.16 ± 0.005 μmol/mg protein/min. We infer from these findings that XA‐induced oxidative stress led to decreased biological fitness.
Imperfect referees: Reducing the impact of multiple biases in peer review
Authors: Zhao Yun Wei , Chi Chi‐Hung , van den Heuvel Willem‐Jan
Published: March 2015

Bias in peer review entails systematic prejudice that prevents accurate and objective assessment of scientific studies. The disparity between referees' opinions on the same paper typically makes it difficult to judge the paper's quality. This article presents a comprehensive study of peer review biases with regard to 2 aspects of referees: the static profiles (factual authority and self‐reported confidence) and the dynamic behavioral context (the temporal ordering of reviews by a single reviewer), exploiting anonymized, real‐world review reports of 2 different international conferences in information systems / computer science. Our work extends conventional bias research by considering multiple biases occurring simultaneously. Our findings show that the referees' static profiles are more dominant in peer review bias when compared to their dynamic behavioral context. Of the static profiles, self‐reported confidence improved both conference fitness and impact‐based bias reductions, while factual authority could only contribute to conference fitness‐based bias reduction. Our results also clearly show that the reliability of referees' judgments varies along their static profiles and is contingent on the temporal interval between 2 consecutive reviews.
Data, ideology, and the developing critical program of social informatics
Authors: Marcinkowski Michael
Published: March 2015

The rapidly shifting ideological terrain of computing has a profound impact on Social Informatics's critical and empirical analysis of computerization movements. As these movements incorporate many of the past critiques concerning social fit and situational context leveled against them by Social Informatics research, more subtle and more deeply ingrained modes of ideological practice have risen to support movements of computerization. Among these, the current emphasis on the promises of data and data analytics presents the most obvious ideological challenge. In order to reorient Social Informatics in relation to these new ideological challenges, Louis Althusser's theory of ideology is discussed, with its implications for Social Informatics considered. Among these implications, a changed relationship between Social Informatics's critical stance and its reliance on empirical methods is advanced. Addressed at a fundamental level, the practice of Social Informatics comes to be reoriented in a more distinctly reflective and ethical direction.
The conditions of peak empiricism in big data and interaction design
Authors: Marcinkowski Michael , Fonseca Fred
Published: March 2015

An influx of mechanisms for the collection of large sets of data has prompted widespread consideration of the impact that data analytic methods can have on a number of disciplines. Having an established record of the use of a unique mixture of empirical methods, the work of understanding and designing for user behavior is well situated to take advantage of the advances claimed by “big data” methods. Beyond any straightforward benefit of the use of large sets of data, such an increase in the scale of empirical evidence has far‐reaching implications for the work of empirically guided design. We develop the concept of “peak empiricism” to explain the new role that large‐scale data comes to play in design, one in which data become more than a simple empirical tool. In providing such an expansive empirical setting for design, big data weakens the subjective conditions necessary for empirical insight, pointing to a more performative approach to the relationship between a designer and his or her work. In this, the work of design is characterized as “thinking with” the data in a partnership that weakens not only any sense of empiricism but also the agentive foundations of a classical view of design work.
Actuator and Sensor Fault Reconstructions for Uncertain Lipschitz Nonlinear Systems Based onH∞Observers
Authors: Li Xiaohang , Zhu Fanglai , Xu Liyun
Published: March 2015

This paper considers fault reconstruction problems for a class of uncertain Lipschitz nonlinear systems with actuator faults, sensor faults, and external disturbances. First, by extending the state vector, the original system is transformed into an augmented descriptor system before anobserver, which can decouple the disturbances, is developed. Since the sensor faults become parts of the extended state vector, the descriptor observer can provide not only state estimates but also the sensor fault reconstructions. Second, a second‐order high‐gain sliding mode observer is used to estimate the derivatives of the system outputs in a finite time. Third, using the estimates of the states and the output derivatives, an algebraic actuator fault reconstruction method is proposed. Finally, a simulation example is given to validate the proposed method.
Molecular cloning and transgenic characterization of the genes encoding chalcone synthase and chalcone isomerase from the Tibetan herbal plant Mirabilis himalaica
Authors: Lan Xiaozhong , Quan Hong , Xia Xinli , Yin Weilun , Zheng Weilie
Published: March 2015

Mirabilis himalaica is an endangered medicinal plant species in the Tibetan Plateau. The two genes respectively encoding chalcone synthase (MhCHS) and chalcone isomerase (MhCHI) were isolated and characterized from M. himalaica. The sequence analysis revealed that the two genes were similar with their corresponding homologous genes in other plants. The tissue profiles showed that both MhCHS and MhCHI had higher expression levels in roots than in stems and leaves. Transgenic hairy root cultures respectively with overexpressing MhCHS and MhCHI were established. The genomic PCR detection confirmed the authority of transgenic hairy root lines, in which either MhCHS or MhCHI expression levels were much higher than that in non‐transgenic hairy root line. Finally, the HPLC detection results demonstrated that the rotenoid contents in MhCHS/MhCHI‐transformed hairy root lines were enhanced. This study provided two candidate genes that could be used to genetic engineering rotenoid biosynthesis in M. himalaica and an alternative method to produce rotenoid using transgenic hairy root cultures.
In silico analysis of human Toll‐like receptor 7 ligand binding domain
Authors: Gupta Chhedi Lal , Akhtar Salman , Sayyed Uzma , Pathak Neelam , Bajpai Preeti
Published: March 2015

Toll‐like receptors recognizing pathogen‐associated molecular patterns are preface actors for innate immunity. Among them TLR7 is a transmembrane protein playing very crucial role in the signaling pathways involved in innate immunity by recognizing viral ssRNA and specific small molecule agonists. The unavailability of experimental 3D structure of this receptor till date hampers the focused exploration of TLR7 interaction with its ligands. However, several proteins possessing high homology domain enabled us to construct a reliable 3D model of hTLR7 ECD, which was employed to generate the homodimer model using protein–protein docking strategy. Further molecular docking studies between developed homodimer model and ligands were performed to explore the most preferred site of hTLR7 ECD interacting with ligands. The comparative analysis of docking energies and protein–ligand interactions of all the ligands revealed resiquimod as the prominent agonist. Furthermore, molecular interactions between protein–ligand complexes suggested LRR15 and LRR16 region of hTLR7 ECD as the most preferential site for ligand binding. The Ser434 and Gly437 of LRR15 region of hTLR7 were found to be conserved with Drosophila Toll protein. The obtained complex model may lead to a better understanding of TLR7 functioning along with its inheritance from invertebrates to mammals.
Optimization of medium components and physicochemical parameters to simultaneously enhance microbial growth and production of lypolitic enzymes by Stenotrophomonas sp.
Authors: Mazzucotelli Cintia Anabela , Agüero María Victoria , del Rosario Moreira María , Ansorena María Roberta
Published: March 2015

The optimization of lipase and esterase production (LP and EP) and bacterial growth (BG) of a Stenotrophomonas sp. strain was developed. For this purpose, the effect of five different medium components and three physicochemical parameters were evaluated using a Plackett–Burman statistical design. Among eight variables, stirring speed, pH, and peptone concentration were found to be the most effective factors on the three responses under evaluation. An optimization study applying Box–Behnken response surface methodology was used to study the interactive effects of the three selected variables on LP/EP and microorganism growth. Predicted models were found to be significant with high regression coefficients (90%–99%). By using the desirability function approach, the optimum condition applying simultaneous optimization of the three responses under study resulted to be: stirring speed of 100 rpm, pH of 7.5, and a peptone concentration of 10 g/L, with a desirability value of 0.977. Under these optimal conditions, it is possible to achieve in the optimized medium a 15‐fold increase in esterase productivity, a 117‐fold increase in lipase production, and a 9‐log CFU/mL increase in BG, compared with the basal medium without agitation.
Serial block face‐scanning electron microscopy: A tool for studying embryonic development at the cell–matrix interface
Authors: Starborg Tobias , Kadler Karl E.
Published: March 2015

Studies of gene regulation, signaling pathways, and stem cell biology are contributing greatly to our understanding of early embryonic vertebrate development. However, much less is known about the events during the latter half of embryonic development, when tissues comprising mostly extracellular matrix (ECM) are formed. The matrix extends far beyond the boundaries of individual cells and is refractory to study by conventional biochemical and molecular techniques; thus major gaps exist in our knowledge of the formation and three‐dimensional (3D) organization of the dense tissues that form the bulk of adult vertebrates. Serial block face‐scanning electron microscopy (SBF‐SEM) has the ability to image volumes of tissue containing numerous cells at a resolution sufficient to study the organization of the ECM. Furthermore, whereas light microscopy was once relatively straightforward and electron microscopy was performed in specialist laboratories, the tables are turned; SBF‐SEM is relatively straightforward and is becoming routine in high‐end resolution studies of embryonic structures in vivo. In this review, we discuss the emergence of SBF‐SEM as a tool for studying embryonic vertebrate development. Birth Defects Research (Part C) 105:9–18, 2015. © 2015 Wiley Periodicals, Inc.
Design of experiments reveals critical parameters for pilot‐scale freeze‐and‐thaw processing of L‐lactic dehydrogenase
Authors: Roessl Ulrich , Humi Sebastian , Leitgeb Stefan , Nidetzky Bernd
Published: March 2015

Freezing constitutes an important unit operation of biotechnological protein production. Effects of freeze‐and‐thaw (F/T) process parameters on stability and other quality attributes of the protein product are usually not well understood. Here a design of experiments (DoE) approach was used to characterize the F/T behavior of L‐lactic dehydrogenase (LDH) in a 700‐mL pilot‐scale freeze container equipped with internal temperature and pH probes. In 24‐hour experiments, target temperature between –10 and –38°C most strongly affected LDH stability whereby enzyme activity was retained best at the highest temperature of –10°C. Cooling profile and liquid fill volume also had significant effects on LDH stability and affected the protein aggregation significantly. Parameters of the thawing phase had a comparably small effect on LDH stability. Experiments in which the standard sodium phosphate buffer was exchanged by Tris‐HCl and the non‐ionic surfactant Tween 80 was added to the protein solution showed that pH shift during freezing and protein surface exposure were the main factors responsible for LDH instability at the lower freeze temperatures. Collectively, evidence is presented that supports the use of DoE‐based systematic analysis at pilot scale in the identification of F/T process parameters critical for protein stability and in the development of suitable process control strategies.
Engineering a Bacterial Tape Recorder
Authors: Prokup Alexander , Deiters Alexander
Published: March 2015

A method has been developed to produce and integrate single‐stranded DNA into genomic locations in bacteria in response to exogenous signals. The system functions similarly to a cellular tape recorder by writing information into DNA and reading it at a later time. Much like other cellular memory platforms, its operation is based on DNA recombinase function. However, the scalability and recording capacity have been improved over previous designs. In addition, memory storage was reversible and could be recorded in response to analogue inputs, such as light exposure. This modular memory writing system is an important addition to the genomic editing toolbox available for synthetic biology.
The matricellular protein CCN1 regulates TNF‐α induced vascular endothelial cell apoptosis
Authors: Zhang Jin , Wu Gongxiong , Dai Haibin
Published: March 2015

Due to the epidemic obesity and associated diabetes, the incidence of atherosclerosis is increasing worldwide. Atherosclerosis is a chronic inflammatory disease characterized by the hardening and narrowing of arteries with plaques that consist of inflammatory cells, dead endothelial cells, lipids, and often hyper proliferated vascular smooth muscle cells. During the development of atherosclerosis, vascular endothelial cell (EC) apoptosis induced by the adipokine tumor necrosis factor alpha (TNF‐α), is an early event in the plaque formation. However, TNF‐α alone is not sufficient to induce apoptosis of endothelial cells. Recent studies suggested that the matricellular protein CCN family member 1 (CCN1) involves in endothelial cell dysfunction besides its well‐known angiogenic function during tissue repair by promoting vascular smooth muscle cells proliferation and migration. Herein, we explored the possibility and mechanism of CCN1 in TNF‐α induced endothelial cells apoptosis. Both mRNA and protein levels of CCN1 are found up‐regulated in endothelial cells after TNF‐α treatment. In addition, overexpression of CCN1 promoted endothelial cell apoptosis in the presence of TNF‐α. Furthermore, CCN1 directly up‐regulated the expression of TNF‐α‐target genes, and this up‐regulation required the activation of P53 and NF‐κB both in vivo and in vitro. Taken together, CNN1 regulates TNF‐α induced endothelial cells apoptosis that may underlie poor response to TNF‐α therapy and hence may be a better therapeutic target for preventing vascular dysfunction in obesity.
Different expression levels of spartin cause broad spectrum of cellular consequences in human neuroblastoma cells
Authors: Milewska Malgorzata , Byrne Paula Catherine
Published: March 2015

Hereditary spastic paraplegia describes a diverse group of neurodegenerative conditions characterised by progressive spasticity and weakness of the lower limbs. Mutations in the SPG20 gene encoding spartin cause an autosomal recessive hereditary spastic paraplegia known as Troyer syndrome. To evaluate the cellular consequences of sustained spartin depletion in neuronal cells, we established several clonal SH‐SY5Y cell lines with different level of spartin knockdown. Here, we report that cells with modest spartin downregulation show signs of neuronal differentiation such as increased neuritogenesis and cytoskeleton rearrangement. Interestingly, we also indicate that permanent high level spartin depletion results in impaired cell growth and multiple mitochondrial aberrations, which we speculate, arise as a result of chronic oxidative stress. Our studies demonstrate that the scale of spartin downregulation is the major factor that determines the severity of cellular consequences observed and suggest that there is a critical level of spartin expression which must be maintained for proper cellular functions.
Contribution of Deep Eutectic Solvents for Biomass Processing: Opportunities, Challenges, and Limitations
Authors: Vigier Karine De Oliveira , Chatel Gregory , Jérôme François
Published: March 2015

Since their introduction in 2004, deep eutectic solvents (DESs) have attracted interest in different fields of chemistry. In the case of biomass, DESs are particularly interesting, not only because of their low cost and biodegradability, but also due to their unique property to interact with hydrogen‐bond donors such as renewably sourced polyols or carboxylic acids. Through selected examples, we report the contribution of DESs for the dissolution of biomass, the extraction/purification of bioderived chemicals, and the conversion of carbohydrates to furanic derivatives. In all examples, we discuss how the DES can impact the selectivity of a chemical process and the limitations associated with the use of DES. In particular, impact of the DES viscosity on extraction, the recovery and recycling of DES, and the stabilization of chemical intermediates in DES are among the key aspects that are discussed.
Ruthenium(II) Complexes Containing Lutidine‐Derived Pincer CNC Ligands: Synthesis, Structure, and Catalytic Hydrogenation of CN bonds
Authors: Hernández‐Juárez Martín , López‐Serrano Joaquín , Lara Patricia , Morales‐Cerón Judith P. , Vaquero Mónica , Álvarez Eleuterio , Salazar Verónica , Suárez Andrés
Published: March 2015

A series of Ru complexes containing lutidine‐derived pincer CNC ligands have been prepared by transmetalation with the corresponding silver‐carbene derivatives. Characterization of these derivatives shows both mer and fac coordination of the CNC ligands depending on the wingtips of the N‐heterocyclic carbene fragments. In the presence of tBuOK, the Ru‐CNC complexes are active in the hydrogenation of a series of imines. In addition, these complexes catalyze the reversible hydrogenation of phenantridine. Detailed NMR spectroscopic studies have shown the capability of the CNC ligand to be deprotonated and get involved in ligand‐assisted activation of dihydrogen. More interestingly, upon deprotonation, the Ru‐CNC complex 5 e(BF4) is able to add aldimines to the metal–ligand framework to yield an amido complex. Finally, investigation of the mechanism of the hydrogenation of imines has been carried out by means of DFT calculations. The calculated mechanism involves outer‐sphere stepwise hydrogen transfer to the CN bond assisted either by the pincer ligand or a second coordinated H2 molecule.
Mechanofluorochromic Materials Based on Aggregation‐Induced Emission‐Active Boron Ketoiminates: Regulation of the Direction of the Emission Color Changes
Authors: Yoshii Ryousuke , Suenaga Kazumasa , Tanaka Kazuo , Chujo Yoshiki
Published: March 2015

We report a series of mechanofluorochromic (MFC) compounds based on organoboron complexes with aggregation‐induced emission (AIE) characteristics. We synthesized a variety of boron ketoiminates and investigated the effect of the substituents on the optical properties by altering the end groups in the compounds. The synthesized boron ketoiminates showed AIE properties and MFC behavior. Interestingly, the hypsochromic and bathochromic shifts of the emission bands individually observed for boron ketoiminates depended on the chemical structures of the end groups. From the X‐ray diffraction and differential scanning calorimetry analyses, it was confirmed that the MFC property of boron ketoiminates should be derived from a phase transition between crystalline and amorphous states. In addition, the direction of the peak shifts of the emission bands was controlled by the degree of steric hindrance of the end group.
Enantioselective Allylation of (2E,4E)‐2,4‐Dimethylhexadienal: Synthesis of (5R,6S)‐(+)‐Pteroenone
Authors: Koukal Petr , Kotora Martin
Published: March 2015

Allylation, trans‐ and cis‐crotylation of (2E,4E)‐2,4‐dimethylhexadienal, a representative α,β,γ,δ‐unsaturated aldehyde, was carried out under different catalytic and stoichiometric conditions. The reactions catalyzed by organocatalysts TRIP‐PA and N,N′‐dioxides gave the best results with respect to yields, asymmetric induction, and catalyst load in comparison to other procedures. The developed methodology was applied in the enantioselective synthesis of (5R,6S)‐(+)‐pteroenone, a defensive metabolite (ichthyodeterrent) of the Antarctic pteropod Clione antarctica.
Organomagnesium‐Catalyzed Isomerization of Terminal Alkynes to Allenes and Internal Alkynes
Authors: Rochat Raphaël , Yamamoto Koji , Lopez Michael J. , Nagae Haruki , Tsurugi Hayato , Mashima Kazushi
Published: March 2015

Organomagnesium complexes 2 were synthesized from N,N‐dialkylamineimine ligands 1 and dibenzylmagnesium by benzylation of the imine moiety. 3‐Aryl‐1‐propynes reacted with 2 to form the corresponding tetraalkynyl complexes, which acted as catalysts for the transformation of these terminal alkynes into allenes and further to internal alkynes under mild conditions. To the best of our knowledge, this example is the first of an organomagnesium‐catalyzed isomerization of alkynes. Notably, the reactions proceeded through temporally separated autotandem catalysis, thus allowing the isolation of the allene or internal alkyne species in good yields. Mechanistic experiments suggested that the catalytically active tetraalkynyl complexes consist of a tautomeric mixture of alkynyl‐, allenyl‐, and propargylmagnesium species.
Structural, Spectroscopic and Computational Examination of the Dative Interaction in Constrained Phosphine–Stibines and Phosphine–Stiboranes
Authors: Chalmers Brian A. , Bühl Michael , Athukorala Arachchige Kasun S. , Slawin Alexandra M. Z. , Kilian Petr
Published: March 2015

A series of phosphine–stibine and phosphine–stiborane peri‐substituted acenaphthenes containing all permutations of pentavalent groups SbClnPh4–n (5–9), as well as trivalent groups SbCl2, Sb(R)Cl, and SbPh2 (2–4, R=Ph, Mes), were synthesised and fully characterised by single crystal diffraction and multinuclear NMR spectroscopy. In addition, the bonding in these species was studied by DFT computational methods. The P–Sb dative interactions in both series range from strongly bonding to non‐bonding as the Lewis acidity of the Sb acceptor is decreased. In the pentavalent antimony series, a significant change in the P–Sb distance is observed between SbClPh3 and SbCl2Ph2 derivatives 6 and 7, respectively, consistent with a change from a bonding to a non‐bonding interaction in response to relatively small modification in Lewis acidity of the acceptor. In the SbIII series, two geometric forms are observed. The P–Sb bond length in the SbCl2 derivative 2 is as expected for a normal (rather than a dative) bond. Rather unexpectedly, the phosphine–stiborane complexes 5–9 represent the first examples of the σ4P→σ6Sb structural motif.
Orienting Tetramolecular G‐Quadruplex Formation: The Quest for the Elusive RNA Antiparallel Quadruplex
Authors: Mendoza Oscar , Porrini Massimiliano , Salgado Gilmar F. , Gabelica Valérie , Mergny Jean‐Louis
Published: March 2015

DNA and RNA G‐quadruplexes (G4) are unusual nucleic acid structures involved in a number of key biological processes. RNA G‐quadruplexes are less studied although recent evidence demonstrates that they are biologically relevant. Compared to DNA quadruplexes, RNA G4 are generally more stable and less polymorphic. Duplexes and quadruplexes may be combined to obtain pure tetrameric species. Here, we investigated whether classical antiparallel duplexes can drive the formation of antiparallel tetramolecular quadruplexes. This concept was first successfully applied to DNA G4. In contrast, RNA G4 were found to be much more unwilling to adopt the forced antiparallel orientation, highlighting that the reason RNA adopts a different structure must not be sought in the loops but in the G‐stem structure itself. RNA antiparallel G4 formation is likely to be restricted to a very small set of peculiar sequences, in which other structural features overcome the formidable intrinsic barrier preventing its formation.
Palladium‐Catalyzed Oxidative Synthesis of Highly Functionalized Ortholactones
Authors: Baddeley Kate L. , Cao Qun , Muldoon Mark J. , Cook Matthew J.
Published: March 2015

A palladium‐catalyzed oxidative reaction is reported which converts dihydropyrans to their corresponding ortholactone. The products are formed in good to excellent yields with a very high level of chemoselectivity and functional group tolerance. Mechanistic studies confirm that the reaction proceeds by a Wacker‐type mechanism.
Patterned Paper Sensors Printed with Long‐Chain DNA Aptamers
Authors: Carrasquilla Carmen , Little Jessamyn R. L. , Li Yingfu , Brennan John D.
Published: March 2015

There is growing interest in developing printable paper sensors to enable rapid testing of analytes for environmental, food safety, and clinical applications. A major challenge is to find suitable bioinks that are amenable to high‐speed printing and remain functional after printing. We report on a simple and effective approach wherein an aqueous ink composed of megadalton‐sized tandem repeating structure‐switching DNA aptamers (concatemeric aptamers) is used to rapidly create patterned paper sensors on filter paper by inkjet printing. These concatemeric aptamer reporters remain immobilized at the point of printing through strong adsorption but retain sufficient segmental mobility to undergo structure switching and fluorescence signaling to provide both qualitative and quantitative detection of small molecules and protein targets. The convenience of inkjet printing allows for the patterning of internally referenced sensors with multiplexed detection, and provides a generic platform for on‐demand printing of sensors even in remote locations.
Selective Nitrogen Functionalization of Graphene by Bucherer‐Type Reaction
Authors: Chua Chun Kiang , Sofer Zdeněk , Luxa Jan , Pumera Martin
Published: March 2015

The front cover artwork is provided by Pumera’s group at Nanyang Technological University (Singapore) and Sofer’s group at UCT Prague (Czech Republic). The image shows the amino‐functionalization of graphene by the conversion of hydroxyl to amino functional groups against a backdrop of aerial view of New Zealand coastline. Read the full text of the article at 10.1002/chem.201405748.
ChemInform Abstract: Structural Characterization of a New Vacancy Ordered Perovskite Modification Found for Ba3Fe3O7F (BaFeO2.333F0.333): Towards Understanding of Vacancy Ordering for Different Perovskite‐Type Ferrites.
Authors: Clemens Oliver
Published: March 2015

The vacancy ordered perovskite‐type Ba3Fe3O7F (BaFeO2.33F0.33) is prepared by topochemical low‐temperature fluorination of Ba2Fe2O5 using stoichiometric amounts of polyvinylidene difluoride (370 °C, 12 h) followed by annealing in Ar for a defined O content (450 °C, 24 h).
ChemInform Abstract: Crystal Structure and Electronic Properties of Y3AlC3.
Authors: Kotyrba Martin R. , Cuervo‐Reyes Eduardo , Nesper Reinhard
Published: March 2015

Single crystals of Y3AlC3 are prepared from the elements in a Li metal flux in the ratio Li:Y:Al:C = 36:2:2:3 (Nb ampoule, 1250 °C, 7 d; cooling to 600 °C with a rate of 2 °C/h).
ChemInform Abstract: Synthesis, Crystal Structure, and TEM Analysis of Sr19Li44 and Sr3Li2: A Reinvestigation of the Sr—Li Phase Diagram.
Authors: Smetana Volodymyr , Kienle Lorenz , Duppel Viola , Simon Arndt
Published: March 2015

Single crystals of Sr19Li44 (I) and Sr3Li2 (II) are prepared from the elements in Ar (Ta ampoules, 1.
ChemInform Abstract: Syntheses of Two Vanadium Oxide—Fluoride Materials that Differ in Phase Matchability.
Authors: Donakowski Martin D. , Gautier Romain , Lu Hongcheng , Tran T. Thao , Cantwell Jacqueline R. , Halasyamani P. Shiv , Poeppelmeier Kenneth R.
Published: March 2015

Non‐centrosymmetric NaVOF4(H2O) (I) and NaVO2‐xF2+x (II; x = 1/3) are prepared from an 1:1:4 molar mixture of V2O5, NaCl, and HF (teflon container, 100 °C, 30 min for (I) and 150 °C, 24 h for (II)).
ChemInform Abstract: A Facile Strategy to Achieve High Conduction and Excellent Chemical Stability of Lithium Solid Electrolytes.
Authors: Song Shufeng , Lu Jia , Zheng Feng , Duong Hai M. , Lu Li
Published: March 2015

Substitution of Cl for O based on the concept of bottleneck size and binding energy is performed for Li10.5‐xSi/Ge1.5P1.5Clx O12‐x (x = 0.05‐1).
ChemInform Abstract: Unification of Catalytic Water Oxidation and Oxygen Reduction Reactions: Amorphous Beat Crystalline Cobalt Iron Oxides.
Authors: Indra Arindam , Menezes Prashanth W. , Sahraie Nastaran Ranjbar , Bergmann Arno , Das Chittaranjan , Tallarida Massimo , Schmeisser Dieter , Strasser Peter , Driess Matthias
Published: March 2015

Controlled solvothermal preparation of highly crystalline CoFe2O4 (I) and amorphous CoFe2On (II; n ≈3.66) are performed by using aqueous resp.
ChemInform Abstract: Synthesis and Characterization of Fluorodinitroamine, FN(NO2)2.
Authors: Christe Karl O. , Wilson William W. , Belanger‐Chabot Guillaume , Haiges Ralf , Boatz Jerry A. , Rahm Martin , Prakash G. K. Surya , Saal Thomas , Hopfinger Mathias
Published: March 2015

The title compound is synthesized by reaction of NF4SbF6 and KN(NO2)2 using SO2 or MeCN as solvent (vacuum, ‐196 °C followed by warming to the melting point of the solvent) and characterized by multinuclear NMR and Raman spectroscopy, and quantum chemical DFT calculations.
ChemInform Abstract: Mercury(II) Nitroprusside: A Framework with an Unusual Topology.
Authors: Cano A. , Osiry H. , Reguera L. , Lemus‐Santana A. A. , Reguera E.
Published: March 2015

Hg[Fe(CN)5NO] is precipitated from aqueous solutions of Na2[Fe(CN)5NO] and Hg(NO3)2 followed by aging in the dark for 3 days.
ChemInform Abstract: High Pressure Synthesis and Properties of Bi0.5Pb0.5CrO3: A Novel Cr4+/Cr3+ Perovskite.
Authors: Pirrotta Ivan , Schmidt Rainer , Dos Santos‐Garcia Antonio J. , Garcia‐Hernandez Mar , Moran Emilio , Alario‐Franco Miguel. A.
Published: March 2015

The Bi0.5Pb0.5CrO3 double perovskite is prepared by high pressure reaction of stoichiometric amounts of PbO, Bi2O3, Cr2O3, and CrO2 (Pt capsule in a belt‐type press, 70 kbar, 1000 °C, 15 min).
ChemInform Abstract: A Strategy for the Preparation of Thioantimonates Based on the Concept of Weak Acids and Corresponding Strong Bases.
Authors: Anderer Carolin , Delwa de Alarcon Natalie , Naether Christian , Bensch Wolfgang
Published: March 2015

The layered compounds (III) and (V) are synthesized by a new hydrothermal synthetic approach which is based on the in situ formation of a basic medium by the reaction between the strong base SbS43‐ and the weak acid H2O.
ChemInform Abstract: Highly Diastereoselective Generation of Various 3,3‐Disubstituted Allyl Boronates for the Stereospecific Construction of Quaternary Centers.
Authors: Biggs Robyn Aryn , Lambadaris Maria , Ogilvie William W.
Published: March 2015

Various dialkyl substituted allyl boronates are condensed with aromatic and aliphatic aldehydes.
ChemInform Abstract: Organocatalytic Asymmetric Vinylogous Michael Addition of 3‐Alkylidene Oxindoles to α‐Substituted β‐Nitroacrylates: Facile Construction of a Chiral All‐Carbon Quaternary Center.
Authors: Zhong Yuan , Ma Shixiong , Xu Zhaoqing , Chang Min , Wang Rui
Published: March 2015

The stereocenters and alkene geometries of the products (III), (V), and (VII) are precisely controlled by the employed bifunctional squaramide catalyst.
ChemInform Abstract: Gallium‐Assisted Transfer Hydrogenation of Alkenes.
Authors: Michelet Bastien , Bour Christophe , Gandon Vincent
Published: March 2015

Optimized reaction conditions including 1,4‐cyclohexadiene as hydrogen source in combination with a gallium carbene complex catalyst allow hydrogenative cyclization, hydroarylation, and reduction of olefins.
ChemInform Abstract: Catalytic and Direct Methyl Sulfonylation of Alkenes and Alkynes Using a Methyl Sulfonyl Radical Generated from a DMSO, Dioxygen and Copper System.
Authors: Jiang Yaojia , Loh Teck‐Peng
Published: March 2015

Alkyl substituted alkene analogues of (I) are unreactive.
ChemInform Abstract: Sulfonamide‐Promoted Palladium(II)‐Catalyzed Alkylation of Unactivated Methylene C(sp3)—H Bonds with Alkyl Iodides.
Authors: Chen Kai , Shi Bing‐Feng
Published: March 2015

The Pd(II)‐catalyzed alkylation of unactivated β‐methylene C(sp3)‐H bonds of α‐amino acid substrates having a 8‐aminoquinoline amide auxiliary is described.