bluuebunny/crossref_metadata_2025_split huggingface dataset:
Non‐hazardous biocatalytic oxidation in Nylon‐9 monomer synthesis on a 40 g scale with efficient downstream processing
Authors: Milker Sofia , Fink Michael J. , Rudroff Florian , Mihovilovic Marko D. 
Published: April 2017

ABSTRACTThis paper describes the development of a biocatalytic process on the multi‐dozen gram scale for the synthesis of a precursor to Nylon‐9, a specialty polyamide. Such materials are growing in demand, but their corresponding monomers are often difficult to synthesize, giving rise to biocatalytic approaches. Here, we implemented cyclopentadecanone monooxygenase as an Escherichia coli whole‐cell biocatalyst in a defined medium, together with a substrate feeding–product removal concept, and an optimized downstream processing (DSP). A previously described hazardous peracid‐mediated oxidation was thus replaced with a safe and scalable protocol, using aerial oxygen as oxidant, and water as reaction solvent. The engineered process converted 42 g (0.28 mol) starting material ketone to the corresponding lactone with an isolated yield of 70% (33 g), after highly efficient DSP with 95% recovery of the converted material, translating to a volumetric yield of 8 g pure product per liter. Biotechnol. Bioeng. 2017;114: 1670–1678. © 2017 Wiley Periodicals, Inc.
Identification and control of novel growth inhibitors in fed‐batch cultures of Chinese hamster ovary cells
Authors: Mulukutla Bhanu Chandra , Kale Jaitashree , Kalomeris Taylor , Jacobs Michaela , Hiller Gregory W. 
Published: April 2017

ABSTRACTChinese hamster ovary (CHO) cells in culture are known to consume large amounts of nutrients and divert most of them toward byproducts, some of which, including lactate and ammonia, are known to be toxic in nature. Glucose limitation strategies can successfully control lactate accumulation in fed‐batch cultures yielding higher peak cell densities and titers. Interestingly, even in such optimized cultures, cell growth slows and eventually stops, indicating the emergence of other factors that negatively affect cell growth. In this study, we employed omics techniques to identify and quantify nine compounds that are intermediates or byproducts of amino acid metabolism, and accumulate in fed‐batch cultures. Treatment with these compounds either individually or in a combined fashion resulted in partial or complete cell growth inhibition. Careful control of selected amino acid concentrations between one‐half and one millimolar during the growth phase of fed‐batch cultures reduced accumulation of the inhibitory metabolites and allowed for higher peak cell densities and increased productivity. Biotechnol. Bioeng. 2017;114: 1779–1790. © 2017 Wiley Periodicals, Inc.
An in vitro synthetic biology platform for the industrial biomanufacturing of myo‐inositol from starch
Authors: You Chun , Shi Ting , Li Yunjie , Han Pingping , Zhou Xigui , Zhang Yi‐Heng Percival 
Published: April 2017

ABSTRACTMyo‐Inositol (vitamin B8) is widely used in the drug, cosmetic, and food & feed industries. Here, we present an in vitro non‐fermentative enzymatic pathway that converts starch to inositol in one vessel. This in vitro pathway is comprised of four enzymes that operate without ATP or NAD+ supplementation. All enzyme BioBricks are carefully selected from hyperthermophilic microorganisms, that is, alpha‐glucan phosphorylase from Thermotoga maritima, phosphoglucomutase from Thermococcus kodakarensis, inositol 1‐phosphate synthase from Archaeoglobus fulgidus, and inositol monophosphatase from T. maritima. They were expressed efficiently in high‐density fermentation of Escherichia coli BL21(DE3) and easily purified by heat treatment. The four‐enzyme pathway supplemented with two other hyperthermophilic enzymes (i.e., 4‐α‐glucanotransferase from Thermococcus litoralis and isoamylase from Sulfolobus tokodaii) converts branched or linear starch to inositol, accomplishing a very high product yield of 98.9 ± 1.8% wt./wt. This in vitro (aeration‐free) biomanufacturing has been successfully operated on 20,000‐L reactors. Less costly inositol would be widely added in heath food, low‐end soft drink, and animal feed, and may be converted to other value‐added biochemicals (e.g., glucarate). This biochemical is the first product manufactured by the in vitro synthetic biology platform on an industrial scale. Biotechnol. Bioeng. 2017;114: 1855–1864. © 2017 Wiley Periodicals, Inc.
Modulation and modeling of monoclonal antibody N‐linked glycosylation in mammalian cell perfusion reactors
Authors: Karst Daniel J. , Scibona Ernesto , Serra Elisa , Bielser Jean‐Marc , Souquet Jonathan , Stettler Matthieu , Broly Hervé , Soos Miroslav , Morbidelli Massimo , Villiger Thomas K. 
Published: April 2017

ABSTRACTMammalian cell perfusion cultures are gaining renewed interest as an alternative to traditional fed‐batch processes for the production of therapeutic proteins, such as monoclonal antibodies (mAb). The steady state operation at high viable cell density allows the continuous delivery of antibody product with increased space‐time yield and reduced in‐process variability of critical product quality attributes (CQA). In particular, the production of a confined mAb N‐linked glycosylation pattern has the potential to increase therapeutic efficacy and bioactivity. In this study, we show that accurate control of flow rates, media composition and cell density of a Chinese hamster ovary (CHO) cell perfusion bioreactor allowed the production of a constant glycosylation profile for over 20 days. Steady state was reached after an initial transition phase of 6 days required for the stabilization of extra‐ and intracellular processes. The possibility to modulate the glycosylation profile was further investigated in a Design of Experiment (DoE), at different viable cell density and media supplement concentrations. This strategy was implemented in a sequential screening approach, where various steady states were achieved sequentially during one culture. It was found that, whereas high ammonia levels reached at high viable cell densities (VCD) values inhibited the processing to complex glycan structures, the supplementation of either galactose, or manganese as well as their synergy significantly increased the proportion of complex forms. The obtained experimental data set was used to compare the reliability of a statistical response surface model (RSM) to a mechanistic model of N‐linked glycosylation. The latter outperformed the response surface predictions with respect to its capability and reliability in predicting the system behavior (i.e., glycosylation pattern) outside the experimental space covered by the DoE design used for the model parameter estimation. Therefore, we can conclude that the modulation of glycosylation in a sequential steady state approach in combination with mechanistic model represents an efficient and rational strategy to develop continuous processes with desired N‐linked glycosylation patterns. Biotechnol. Bioeng. 2017;114: 1978–1990. © 2017 Wiley Periodicals, Inc.
Development of Tetramethylenedisulfotetramine (TETS) Hapten Library: Synthesis, Electrophysiological Studies, and Immune Response in Rabbits.
Authors: Barnych Bogdan , Vasylieva Natalia , Joseph Tom , Hulsizer Susan , Nguyen Hai M. , Cajka Tomas , Pessah Isaac , Wulff Heike , Gee Shirley J. , Hammock Bruce D. 
Published: April 2017

AbstractThere is a need for fast detection methods for the banned rodenticide tetramethylenedisulfotetramine (TETS), a highly potent blocker of the γ‐aminobutyric acid (GABAA) receptors. General synthetic approach toward two groups of analogues was developed. Screening of the resulting library of compounds by FLIPR or whole‐cell voltage‐clamp revealed that, despite the structural differences, some of the TETS analogues retained GABAA receptor inhibition; however, their potency was an order of magnitude lower. Antibodies raised in rabbits against some of the TETS analogues conjugated to protein recognized free TETS and will be used for the development of an immunoassay for TETS.
Synthesis and Properties of Salicylaldehydes Fine‐Tuned by Modular Assembly using “Plug‐and‐Socket”‐Type Extendibility
Authors: Houjou Hirohiko , Suzuki Yoshikazu , Shen Qian‐Wen , Yoshikawa Isao , Mutai Toshiki 
Published: April 2017

AbstractA salicylaldehyde derivative bearing four pyridine arms, 3,5‐bis(N,N‐bis(2‐pyridylmethyl)aminomethyl)‐2,4‐dihydroxybenzaldehyde (Hbpsal) as a “socket”, was prepared and used to derive a series of zinc complexes with various extra anions “plugged” into their vacant site. The crystal structure and 1H NMR spectra were noticeably influenced by the extra anions, allowing fine‐tuning of the properties by “plug‐and‐socket”‐type modification. Similar to unsubstituted salicylaldehyde, the zinc complexes reacted with primary amines to afford Schiff‐base compounds. Because of the potential chirality around the coordination sphere, reaction with a chiral amine resulted in an equilibrium system between diastereomers, the potential of which as chiral sources tunable by the extra anions is discussed. Some of the complexes were further converted into zinc‐ or nickel‐salphen (=N,N‐bis(salicylidene)‐1,2‐phenylenediamine) complexes. The electrochemical properties of the nickel complex were slightly modified by the extra anions, whereas the photophysical properties of the zinc complex appeared unchanged.
2H→1T Phase Engineering of Layered Tantalum Disulfides in Electrocatalysis: Oxygen Reduction Reaction
Authors: Luxa Jan , Mazánek Vlastimil , Pumera Martin , Lazar Petr , Sedmidubský David , Callisti Mauro , Polcar Tomáš , Sofer Zdeněk 
Published: April 2017

AbstractTremendous attention is currently being paid to renewable sources of energy. Transition‐metal dichalcogenides (TMDs) have been intensively studied for their promising catalytic activities in the hydrogen evolution reaction (HER) and the oxygen reduction reaction (ORR). In this fundamental work, we explored the catalytic properties of TMD family members 2H TaS2 and 1T TaS2. Our findings reveal that both polytypes exhibit poor HER performance, which is even more pronounced after electrochemical reduction/oxidation. Our experimental data show that 1T TaS2 has a lower overpotential at a current density of −10 mA cm−1, despite theoretical DFT calculations that indicated that the more favorable free energy of hydrogen adsorption should make “perfect” 2H TaS2 a better HER catalyst. Thorough characterization showed that the higher conductivity of 1T TaS2 and a slightly higher surface oxidation of 2H TaS2 explains this discrepancy. Moreover, changes in the catalytic activity after electrochemical treatment are addressed here. For the ORR in an alkaline environment, the electrochemical treatment led to an improvement in catalytic properties. With onset potentials similar to that of Pt/C catalysts, TaS2 was found to be an efficient catalyst for the ORR, rather than for proton reduction, in contrast to the behavior of Group 6 layered TMDs.
Nodular oncocytic hyperplasia: Can cytomorphology allow for the preoperative diagnosis of a nonneoplastic salivary disease?
Authors: Rooper Lisa M. , Onenerk Mine , Siddiqui Momin T. , Faquin William C. , Bishop Justin A. , Ali Syed Z. 
Published: April 2017

BACKGROUNDNodular oncocytic hyperplasia (oncocytosis) of the salivary glands is a benign process that does not inherently require surgical excision. However, cytologic findings in fine‐needle aspiration (FNA) of oncocytosis cases have not been well characterized previously, limiting preoperative identification.METHODSAll available cases of oncocytosis with corresponding FNA specimens were identified from the pathology archives of 3 academic institutions. Clinical, cytologic, and histologic findings were tabulated for all cases.RESULTSTwelve cases of oncocytosis were identified from 11 patients, including 11 parotid FNA specimens and 1 submandibular FNA specimen. On the original diagnoses, 6 specimens were classified as benign, 4 as atypical, and 2 as nondiagnostic. Oncocytosis was listed in the differential diagnosis in only 1 case. Among diagnostic aspirates, 8 demonstrated low cellularity and 2 demonstrated moderate cellularity. All 10 cases demonstrated oncocytic cells in small to medium groups, with single cells in just 1 case. Spindled and squamous morphology were each noted in 3 cases. Four cases demonstrated cystic change and 1 showed background mucin without goblet cells. No necrosis or mitoses were observed.CONCLUSIONSAlthough oncocytosis demonstrates some overlap with Warthin tumor and oncocytoma, it lacks the diagnostic findings specific to oncocytic salivary gland malignancies such as salivary duct carcinoma, acinic cell carcinoma, mammary analog secretory carcinoma, and mucoepidermoid carcinoma. Despite current limitations in the understanding of oncocytic salivary gland lesions, the presence of a paucicellular specimen comprised of small groups of oncocytic cells should raise the possibility of oncocytosis in the differential diagnosis and can favor it in elderly patients with multiple salivary nodules. Cancer Cytopathol 2017;125:627‐34. © 2017 American Cancer Society.
CO2‐Assisted Solution‐Phase Selective Assembly of 2D WS2‐WO3⋅H2O and 1T‐2H MoS2 to Desirable Complex Heterostructures
Authors: Ren Yumei , Xu Qun , Wang Chongze , Zheng Xiaoli , Jia Yu , Qi Yuhang , Zhou Yunchun , Yang Xinan , Zhang Zhenyu 
Published: April 2017

AbstractPrecise control of the lateral and vertical integration of two‐dimensional (2D) heterostructures is exciting for novel electronic and photovoltaic applications. Fabricating assemblies of high‐quality heterostructures with desirable compositions and sequences is challenging. In this work, with the assistance of supercritical CO2 (SC CO2), we successfully prepared the complex heterostructures of WS2‐WO3⋅H2O/1T‐2H MoS2 with selective stacking assembly. Thanks to the unique properties of SC CO2, which can help to construct a unique solvent system where the hydrophilic or hydrophobic structure for the 2D layer heterostructure can be chosen, 2H‐WS2/2H‐MoS2 assemblies are formed efficiently as the preferred van der Waals heterojunctions. A superior photoelectrochemical activity toward hydrogen evolution based on such the quaternary heterostructures is achieved due to their strong interlayer electronic coupling as well as the increased conductivity and active sites in the heterostructures.
Magnetic Response of Aromatic Rings Under Rotation: Aromatic Shielding Cone of Benzene Upon Different Orientations of the Magnetic Field
Authors: Papadopoulos A. G. , Charistos N. D. , Muñoz‐Castro A. 
Published: April 2017

AbstractThe induced shielding cone is one of the most characteristic aspects of aromatic species. Herein, we explore its behavior under different orientations of the applied magnetic field by evaluating the overall and dissected π‐ and σ‐electron contributions. Our results shed light onto the orientation dependence behavior of the shielding cone, unraveling a characteristic pattern upon rotation of the aromatic ring. This pattern decreases the long range of the magnetic response, such that it resembles the behavior under constant molecular tumbling in solution.
Macroporous Silica with Thick Framework for Steam‐Stable and High‐Performance Poly(ethyleneimine)/Silica CO2 Adsorbent
Authors: Min Kyungmin , Choi Woosung , Choi Minkee 
Published: April 2017

AbstractPoly(ethyleneimine) (PEI)/silica has been widely studied as a solid adsorbent for post‐combustion CO2 capture. In this work, a highly macroporous silica (MacS), synthesized by secondary sintering of fumed silica, is compared with various mesoporous silicas with different pore structures as a support for PEI. The silicas with large pore diameter and volume enabled high CO2 adsorption kinetics and capacity, because pore occlusion by the supported PEI was minimized. The steam stability of the silica structures increased with the silica wall thickness owing to suppressed framework ripening. The silicas with low steam stability showed rapid leaching of PEI, which indicated that the PEI squeezed out of the collapsed silica pores leached more readily. Consequently, MacS that had an extra‐large pore volume (1.80 cm3 g−1) and pore diameter (56.0 nm), and a thick wall (>10 nm), showed the most promising CO2 adsorption kinetics and capacity as well as steam stability.
A Blue Diketopyrrolopyrrole Sensitizer with High Efficiency in Nickel‐Oxide‐based Dye‐Sensitized Solar Cells
Authors: Farré Yoann , Raissi Mahfoudh , Fihey Arnaud , Pellegrin Yann , Blart Errol , Jacquemin Denis , Odobel Fabrice 
Published: April 2017

AbstractWe prepared a series of four new diketopyrrolopyrroles (DPPs)‐based sensitizers that exhibit high‐molar extinction coefficients, extended absorption into the long wavelengths, and well‐suited photoredox properties to act as sensitizers in p‐type dye‐sensitized solar cells (p‐DSSCs). These new DPP dyes, composed of a thienyl DPP core, are substituted on one end either by a thiophene carboxylic (Th) or a 4,4′‐[(phenyl)aza]dibenzoic acid as anchoring group and, on the other extremity, either by a proton or a naphthalene diimide (NDI) moiety. These new dyes were completely characterized by absorption and emission spectroscopy along with electrochemistry and they were modeled by time‐dependent DFT (TD‐DFT) quantum chemical calculations. The photovoltaic study in p‐DSSC with iodine‐based electrolyte reveals that the Th‐DPP‐NDI dye is particularly efficient (Jsc=7.38 mA cm−2; Voc=147 mV; FF=0.32; η=0.35 %) and quite active in the low‐energy region of the solar spectrum (above 700 nm), where only a few NiO dyes are effective. To illustrate the potential of DPP dyes in photocathodes, we designed a highly efficient tandem DSSC composed of a TiO2 photoanode sensitized by the dye D35 and a NiO photocathode sensitized by Th‐DPP‐NDI. This tandem DSSC gives the highest performances ever reported (Jsc=6.73 mA cm−2; Voc=910 mV; η=4.1 %) and, importantly, the tandem cell outcompetes with the sub‐cells.
Determining the ultimate load of historic masonry arches by using eccentricity charts
Authors: Dunjic Viktor , Rudisch Andreas , Wittner Valentina , Malcher Benjamin , Kolbitsch Andreas 
Published: April 2017

AbstractThe eccentricity charts presented in this paper have been developed on the basis of experimental investigations in order to enable a realistic calculation method of the ultimate load of flat brickwork vaulted floors with standard structural software. The vault is modelled as a three‐hinged arch with eccentric hinges in order to thus represent the non‐linear behaviour of the load‐bearing structure. Furthermore the hinge configuration, which is adapted with the eccentricity charts, takes into account the degree of plastification of historic masonry, existing load‐induced damage, any displacement of the abutments and the location of the thrust line.Two examples are described to explain the applicability of this method, and the results are compared with results from other modelling approaches. This makes clear that the eccentricity charts enable realistic structural analysis of flat brickwork vaults with various geometries and with highly efficient use of time.
A worldwide phylogeography of the whiteworm lichens Thamnolia reveals three lineages with distinct habitats and evolutionary histories
Authors: Onuţ‐Brännström Ioana , Tibell Leif , Johannesson Hanna 
Published: April 2017

AbstractThamnolia is a lichenized fungus with an extremely wide distribution, being encountered in arctic and alpine environments in most continents. In this study, we used molecular markers to investigate the population structure of the fungal symbiont and the associated photosynthetic partner of Thamnolia. By analyzing molecular, morphological, and chemical variation among 253 specimens covering the species distribution range, we revealed the existence of three mycobiont lineages. One lineage (Lineage A) is confined to the tundra region of Siberia and the Aleutian Islands, a second (Lineage B) is found in the high alpine region of the Alps and the Carpathians Mountains, and a third (Lineage C) has a worldwide distribution and covers both the aforementioned ecosystems. Molecular dating analysis indicated that the split of the three lineages is older than the last glacial maximum, but the distribution ranges and the population genetic analyses suggest an influence of last glacial period on the present‐day population structure of each lineage. We found a very low diversity of Lineage B, but a higher and similar one in Lineages A and C. Demographic analyses suggested that Lineage C has its origin in the Northern Hemisphere, possibly Scandinavia, and that it has passed through a bottleneck followed by a recent population expansion. While all three lineages reproduce clonally, recombination tests suggest rare or past recombination in both Lineages A and C. Moreover, our data showed that Lineage C has a comparatively low photobiont specificity, being found associated with four widespread Trebouxia lineages (three of them also shared with other lichens), while Lineages A and B exclusively harbor T. simplex s. lat. Finally, we did not find support for the recognition of taxa in Thamnolia based on either morphological or chemical characters.
Vegetation responses to an ecological water conveyance project in the lower reaches of the Heihe River basin
Authors: Zhang Shuhua , Ye Zhaoxia , Chen Yaning , Xu Yufeng 
Published: April 2017

AbstractThe lower reaches of the Heihe River basin (HHLR), which is located in arid and semiarid areas of Northwest China, has experienced severe environmental deterioration in the past several decades. The ecological water conveyance project was initiated by the Chinese Government in 2000 to address this degraded ecosystem.In this paper, runoff, vegetation changes, and the relationship between runoff and vegetation in different regions were explored after the project, normalized difference vegetation index (NDVI), as a proxy of vegetation cover. For the entire lower reaches, NDVI and runoff exhibit an increasing trend after the project. In spatial, 44% of the vegetation‐covered area is significantly increased; whereas, 37% also exhibits an insignificant increasing trend. Moreover, 15% of the vegetation‐covered area shows an insignificant decreasing trend, and 5% exhibits a significant decrease. Overall, vegetation in HHLR improved after the ecological water conveyance project. The maximum time lag for NDVI along the east river and runoff from the east river, NDVI in the Ejina Oasis and runoff from the east river and the east canal, and NDVI along the west river and runoff from the west river was 4, 4, 3, and 6 years, respectively. However, runoff from last year had a significant influence on the current year's NDVI for the east river and the east canal. Meanwhile, autumn runoff shows a significant influence on the next year's NDVI, and spring runoff is important to the current year's NDVI. So we concluded that it is reasonable to convey more water into HHLR in autumn and spring.