bluuebunny/crossref_metadata_2025 huggingface dataset:
Hydroalumination of Alkenes and Alkynes
Authors: Baroni Adriano C. M. , Arruda Carla C. P. , Carvalho Diego B.
Published: March 2017

This chapter aims to show the main applications of hydroalumination of alkenes and alkynes. The hydroalumination of terminal alkynes, symmetrical and asymmetrical internal alkynes, silyl acetylenes, tin acetylenes, as well as the preparation of (E) and (Z) vinyl organochalcogens are discussed in detail. The limitations of the hydroalumination of alkynes, with emphasis on chemo‐, regio‐, and stereo‐selectivity, are also covered. Finally, some applications of this reaction for the preparation of pharmaceuticals and natural products are also presented.
Enolates in Macromolecular Science: Current Situation and Future Outlook
Authors: Lecomte Philippe , Jérôme Christine
Published: March 2017

This chapter is in part an update on another one published in the Patai Series. This review describes different enolate‐based reactions implemented for the synthesis of polymers. First, the substitution of lactones in the α position through enolates is reported with the aim of highlighting their ring‐opening polymerization toward degradable polyesters. Second, special attention is paid on the anionic polymerization of acrylates and methacrylates, involving enolates in the initiation and propagation steps. The impact of transfer and termination reactions is detailed. Several processes allowing the synthesis of polyacrylates and polymethacrylates with narrow molar‐mass distribution as well as high and predetermined molar masses are reported, such as ligated anionic polymerization, metal‐free polymerization, and ate‐complex‐mediated polymerization. A last example is group‐transfer polymerization, where enolates are involved as far as nucleophilic catalysts are concerned. The control of tacticity though enolate‐based polymerization is discussed. Third, enolate chemistry is involved in the chemical modification of polymers. A first example relies on the substitution of polymers made up of enolizable esters, typically aliphatic polyesters. Besides, the combination of living polymerization with suitable post‐polymerization techniques is a route to functionalized, star‐shaped, and graft copolymers. The last section describes the use of enolates as catalysts for coordination polymerization. The efficiency of enolate‐based processes with other modern processes is discussed.
The Cluster
A‐I
Solute‐Binding Proteins
Authors: Yukl Erik Thomas
Published: March 2017

Iron, zinc, and manganese are essential nutrients required for the function of a wide variety of proteins and enzymes. Thus, their acquisition from the environment is an absolute necessity. In bacteria, high‐affinity uptake of these metals is undertaken by the cluster A‐I solute‐binding proteins (SBPs) associated with ATP‐binding cassette (ABC) transporters. This process is of particular interest to the biomedical community because bacterial ABC transporters of metals are important virulence factors. Many crystal structures of cluster A‐I SBPs are available in both metal‐bound (holo) and metal‐free (apo) states. These structures provide a wealth of information regarding metal coordination environment, specificity, and conformational changes accompanying metal binding and release. Also presented are early examples of how inhibition of metal transport through ABC transporters is being achieved by disrupting cluster A‐I SBP function.
Dual‐Functionalized Double Carbon Shells Coated Silicon Nanoparticles for High Performance Lithium‐Ion Batteries
Authors: Chen Shuangqiang , Shen Laifa , van Aken Peter A. , Maier Joachim , Yu Yan
Published: March 2017

To address the challenge of huge volume change and unstable solid electrolyte interface (SEI) of silicon in cycles, causing severe pulverization, this paper proposes a “double‐shell” concept. This concept is designed to perform dual functions on encapsulating volume change of silicon and stabilizing SEI layer in cycles using double carbon shells. Double carbon shells coated Si nanoparticles (DCS‐Si) are prepared. Inner carbon shell provides finite inner voids to allow large volume changes of Si nanoparticles inside of inner carbon shell, while static outer shell facilitates the formation of stable SEI. Most importantly, intershell spaces are preserved to buffer volume changes and alleviate mechanical stress from inner carbon shell. DCS‐Si electrodes display a high rechargeable specific capacity of 1802 mAh g−1 at a current rate of 0.2 C, superior rate capability and good cycling performance up to 1000 cycles. A full cell of DCS‐Si//LiNi0.45Co0.1Mn1.45O4 exhibits an average discharge voltage of 4.2 V, a high energy density of 473.6 Wh kg−1, and good cycling performance. Such double‐shell concept can be applied to synthesize other electrode materials with large volume changes in cycles by simultaneously enhancing electronic conductivity and controlling SEI growth.
Dual‐Phase Separation in a Semiconfined System: Monodispersed Heterogeneous Block‐Copolymer Membranes for Cell Encoding and Patterning
Authors: Wang Xiuyu , Feng Xueyan , Ma Guiping , Zhang Di , Chai Yahong , Ge Maofa , Yao Li
Published: March 2017

Block copolymers (BCPs) have the capacity to self‐assemble into a myriad of well‐defined aggregate structures, offering great promise for the construction of drug delivery, photolithographic templates, and complex nanoscale assemblies. A uniqueness of these materials is their propensity to become kinetically frozen in non‐equilibrium states, implying that the process of self‐assembly can be utilized to remodel the resulting structures. Here, a new semiconfined system for processing the BCP self‐assembly is constructed, in which an unusual dual‐phase separation occurs, including nonsolvent‐induced microphase separation and osmotically driven macrophase separation, ultimately yielding heterogeneous BCP membranes. These membranes with cellular dimensions show unique anisotropy that can be used for cell encoding and patterning, which are highly relevant to biology and medicine. This processing method not only provides new levels of tailorability to the structures and encapsulated contents of BCP assemblies, but can also be generalized to other block polymers, particularly those with attractive electronic and/or optical properties.
Mixed Reversible Covalent Crosslink Kinetics Enable Precise, Hierarchical Mechanical Tuning of Hydrogel Networks
Authors: Yesilyurt Volkan , Ayoob Andrew M. , Appel Eric A. , Borenstein Jeffrey T. , Langer Robert , Anderson Daniel G.
Published: March 2017

Hydrogels play a central role in a number of medical applications and new research aims to engineer their mechanical properties to improve their capacity to mimic the functional dynamics of native tissues. This study shows hierarchical mechanical tuning of hydrogel networks by utilizing mixtures of kinetically distinct reversible covalent crosslinks. A methodology is described to precisely tune stress relaxation in PEG networks formed from mixtures of two different phenylboronic acid derivatives with unique diol complexation rates, 4‐carboxyphenylboronic acid, ando‐aminomethylphenylboronic acid. Gel relaxation time and the mechanical response to dynamic shear are exquisitely controlled by the relative concentrations of the phenylboronic acid derivatives. The differences observed in the crossover frequencies corresponding to pKadifferences in the phenylboronic acid derivatives directly connect the molecular kinetics of the reversible crosslinks to the macroscopic dynamic mechanical behavior. Mechanical tuning by mixing reversible covalent crosslinking kinetics is found to be independent of other attributes of network architecture, such as molecular weight between crosslinks.
Architecture of β‐Graphdiyne‐Containing Thin Film Using Modified Glaser–Hay Coupling Reaction for Enhanced Photocatalytic Property of TiO2
Authors: Li Jiaqiang , Xie Ziqian , Xiong Yan , Li Zhenzhu , Huang Qunxing , Zhang Shuqing , Zhou Jingyuan , Liu Rong , Gao Xin , Chen Changguo , Tong Lianming , Zhang Jin , Liu Zhongfan
Published: March 2017

β‐Graphdiyne (β‐GDY) is a member of 2D graphyne family with zero band gap, and is a promising material with potential applications in energy storage, organic electronics, etc. However, the synthesis of β‐GDY has not been realized yet, and the measurement of its intrinsic properties remains elusive. In this work, β‐GDY‐containing thin film is successfully synthesized on copper foil using modified Glaser–Hay coupling reaction with tetraethynylethene as precursor. The as‐grown carbon film has a smooth surface and is continuous and uniform. Electrical measurements reveal the conductivity of 3.47 × 10−6 S m−1 and the work function of 5.22 eV. TiO2@β‐GDY nanocomposite is then prepared and presented with an enhancement of photocatalytic ability compared to pure TiO2.
MOCVD Approach to the Growth of Calcium Copper Titanate (CaCu3Ti4O12) Thin Films: The Role of the Substrate Nature on Film Structural and Dielectrical Properties
Authors: Lo Nigro Raffaella
Published: March 2017

CaCu3Ti4O12 (CCTO) perovskite has been widely investigated because of its excellent dielectric properties, i.e. huge and constant permittivity upon varying temperature and frequencies, which are really attractive in wireless communication devices. These characteristics have been originally demonstrated in single crystals and ceramics. Hence, huge efforts have been focused on the fabrication and investigation of CCTO thin films. First attempts have been performed by pulsed laser deposition technique, nevertheless the chemical vapor deposition methods are preferred for large area industrial production. In this context, here is described the Metal Organic Chemical Vapor Deposition (MOCVD) approach for the growth of CCTO complex oxide. High quality CCTO thin films are fabricated on several substrates, varying from single crystals (LaAlO3 and SrTiO3) to electrodes (Pt and IrO2). The present MOCVD process is based on a molten mixture of the Ca(hfa)2•tetraglyme, Ti(tmhd)2(O‐iPr)2, and Cu(tmhd)2 precursors as multi‐component source. The deposited CCTO films are epitaxial on single crystal substrates, while polycrystalline films have been found on metal electrodes. A correlation among structural/morphological properties of CCTO films with deposition conditions and substrate nature is discussed. Moreover, the effects of the structural properties on the dielectric properties are also investigated.
Asymmetric Hydrogenation of In Situ Generated Isochromenylium Intermediates by Copper/Ruthenium Tandem Catalysis
Authors: Miao Tingting , Tian Zi‐You , He Yan‐Mei , Chen Fei , Chen Ya , Yu Zhi‐Xiang , Fan Qing‐Hua
Published: March 2017

The first asymmetric hydrogenation of in situ generated isochromenylium derivatives is enabled by tandem catalysis with a binary system consisting of Cu(OTf)2and a chiral cationic ruthenium–diamine complex. A range of chiral 1H‐isochromenes were obtained in high yields with good to excellent enantioselectivity. These chiral 1H‐isochromenes could be easily transformed into isochromanes, which represent an important structural motif in natural products and biologically active compounds. The chiral induction was rationalized by density functional theory calculations.
Real‐Time In Vivo Hepatotoxicity Monitoring through Chromophore‐Conjugated Photon‐Upconverting Nanoprobes
Authors: Peng Juanjuan , Samanta Animesh , Zeng Xiao , Han Sanyang , Wang Lu , Su Dongdong , Loong Daniel Teh Boon , Kang Nam‐Young , Park Sung‐Jin , All Angelo Homayoun , Jiang Wenxuan , Yuan Lin , Liu Xiaogang , Chang Young‐Tae
Published: March 2017

Drug toxicity is a long‐standing concern of modern medicine. A typical anti‐pain/fever drug paracetamol often causes hepatotoxicity due to peroxynitrite ONOO−. Conventional blood tests fail to offer real‐time unambiguous visualization of such hepatotoxicity in vivo. Here we report a luminescent approach to evaluate acute hepatotoxicity in vivo by chromophore‐conjugated upconversion nanoparticles. Upon injection, these nanoprobes mainly accumulate in the liver and the luminescence of nanoparticles remains suppressed owing to energy transfer to the chromophore. ONOO− can readily bleach the chromophore and thus recover the luminescence, the presence of ONOO− in the liver leads to fast restoring of the near‐infrared emission. Taking advantages of the high tissue‐penetration capability of near‐infrared excitation/emission, these nanoprobes achieve real‐time monitoring of hepatotoxicity in living animals, thereby providing a convenient screening strategy for assessing hepatotoxicity of synthetic drugs.
Dynamics of O2 Chemisorption on a Flat Platinum Surface Probed by an Alignment‐Controlled O2 Beam
Authors: Ueta Hirokazu , Kurahashi Mitsunori
Published: March 2017

O2 adsorption on Pt surfaces is of great technological importance owing to its relevance to reactions for the purification of car exhaust gas and the oxygen reduction on fuel‐cell electrodes. Although the O2/Pt(111) system has been investigated intensively, questions still remain concerning the origin of the low O2 sticking probability and its unusual energy dependence. We herein clarify the alignment dependence of the initial sticking probability (S0) using the single spin‐rotational state‐selected [(J,M)=(2,2)] O2 beam. The results indicate that, at low translational energy (E0) conditions, direct activated chemisorption occurs only when the O2 axis is nearly parallel to the surface. At high energy conditions (E0>0.5 eV), however, S0 for the parallel O2 decreases with increasing E0 while that of the perpendicular O2 increases, accounting for the nearly energy‐independent O2 sticking probability determined previously by a non‐state‐resolved experiment.
Regimes of Biomolecular Ultrasmall Nanoparticle Interactions
Authors: Boselli Luca , Polo Ester , Castagnola Valentina , Dawson Kenneth A.
Published: March 2017

Ultrasmall nanoparticles (USNPs), usually defined as NPs with core in the size range 1–3 nm, are a class of nanomaterials which show unique physicochemical properties, often different from larger NPs of the same material. Moreover, there are also indications that USNPs might have distinct properties in their biological interactions. For example, recent in vivo experiments suggest that some USNPs escape the liver, spleen, and kidney, in contrast to larger NPs that are strongly accumulated in the liver. Here, we present a simple approach to study the biomolecular interactions at the USNPs bio‐nanointerface, opening up the possibility to systematically link these observations to microscopic molecular principles.
Manganese Silylene Hydride Complexes: Synthesis and Reactivity with Ethylene to Afford Silene Hydride Complexes
Authors: Price Jeffrey S. , Emslie David J. H. , Britten James F.
Published: March 2017

Reaction of the ethylene hydride complex trans‐[(dmpe)2MnH(C2H4)] (1) with Et2SiH2 at 20 °C afforded the silylene hydride [(dmpe)2MnH(=SiEt2)] (2 a) as the trans‐isomer. By contrast, reaction of 1 with Ph2SiH2 at 60 °C afforded [(dmpe)2MnH(=SiPh2)] (2 b) as a mixture of the cis (major) and trans (minor) isomers, featuring a Mn‐H‐Si interaction in the former. The reaction to form 2 b also yielded [(dmpe)2MnH2(SiHPh2)] (3 b); [(dmpe)2MnH2(SiHR2)] (R=Et (3 a) and Ph (3 b)) were accessed cleanly by reaction of 2 a and 2 b with H2, and the analogous reactions with D2 afforded [(dmpe)2MnD2(SiHR2)] exclusively. Both 2 a and 2 b engaged in unique reactivity with ethylene, generating the silene hydride complexes cis‐[(dmpe)2MnH(R2Si=CHMe)] (R=Et (4 a), Ph (4 b)). Compounds trans‐2 a, cis‐2 b, 3 b, and 4 b were crystallographically characterized, and bonding in 2 a, 2 b, 4 a, and 4 b was probed computationally.
Structure of the Complex between a Heparan Sulfate Octasaccharide and Mycobacterial Heparin‐Binding Hemagglutinin
Authors: Huang Teng‐Yi , Irene Deli , Zulueta Medel Manuel L. , Tai Tzu‐Jui , Lain Shih‐Han , Cheng Cheng‐Po , Tsai Ping‐Xi , Lin Shu‐Yi , Chen Zhi‐Geng , Ku Chiao‐Chu , Hsiao Chwan‐Deng , Chyan Chia‐Lin , Hung Shang‐Cheng
Published: March 2017

Heparin‐binding hemagglutinin (HBHA) is a 199 amino acid virulence factor at the envelope of Mycobacterium tuberculosis that contributes to latent tuberculosis. The binding of HBHA to respiratory epithelial cells, which leads to extrapulmonary dissemination of the pathogen, is mediated by cell‐surface heparan sulfate (HS). We report the structural characterization of the HBHA/HS complex by NMR spectroscopy. To develop a model for the molecular recognition, the first chemically synthesized uniformly 13C‐ and 15N‐labeled HS octasaccharide and a uniformly 13C‐ and 15N‐labeled form of HBHA were prepared. Residues 180–195 at the C‐terminal region of HBHA show large chemical shift perturbation upon association with the octasaccharide. Molecular dynamics simulations conforming to the multidimensional NMR data revealed key electrostatic and even hydrophobic interactions between the binding partners that may aid in the development of agents targeting the binding event.
Hyperfine‐Interaction‐Driven Suppression of Quantum Tunneling at Zero Field in a Holmium(III) Single‐Ion Magnet
Authors: Chen Yan‐Cong , Liu Jun‐Liang , Wernsdorfer Wolfgang , Liu Dan , Chibotaru Liviu F. , Chen Xiao‐Ming , Tong Ming‐Liang
Published: March 2017

An extremely rare non‐Kramers holmium(III) single‐ion magnet (SIM) is reported to be stabilized in the pentagonal‐bipyramidal geometry by a phosphine oxide with a high energy barrier of 237(4) cm−1. The suppression of the quantum tunneling of magnetization (QTM) at zero field and the hyperfine structures originating from field‐induced QTMs can be observed even from the field‐dependent alternating‐current magnetic susceptibility in addition to single‐crystal hysteresis loops. These dramatic dynamics were attributed to the combination of the favorable crystal‐field environment and the hyperfine interactions arising from 165Ho (I=7/2) with a natural abundance of 100 %.
Ontogeny of the Human Pelvis
Authors: Verbruggen Stefaan W. , Nowlan Niamh C.
Published: March 2017

The human pelvis has evolved over time into a remarkable structure, optimised into an intricate architecture that transfers the entire load of the upper body into the lower limbs, while also facilitating bipedal movement. The pelvic girdle is composed of two hip bones, os coxae, themselves each formed from the gradual fusion of the ischium, ilium and pubis bones. Unlike the development of the classical long bones, a complex timeline of events must occur in order for the pelvis to arise from the embryonic limb buds. An initial blastemal structure forms from the mesenchyme, with chondrification of this mass leading to the first recognisable elements of the pelvis. Primary ossification centres initiate in utero, followed post‐natally by secondary ossification at a range of locations, with these processes not complete until adulthood. This cascade of events can vary between individuals, with recent evidence suggesting that fetal activity can affect the normal development of the pelvis. This review surveys the current literature on the ontogeny of the human pelvis. Anat Rec, 300:643–652, 2017. © 2017 Wiley Periodicals, Inc.
Bilateral Asymmetry in the Human Pelvis
Authors: Kurki Helen K.
Published: March 2017

Asymmetry of the human axial skeleton has received much less attention that of the limb skeleton. Pelvic morphology is subject to multiple selective factors, including bipedal locomotion and obstetrics, among others, as well as environmental factors such as biomechanical loading. How these various factors influence or restrict asymmetry of the pelvis is unknown and few studies have investigated levels and patterns of pelvic asymmetry. This study examines percentage directional (%DA) and absolute (%AA) asymmetry in 14 bilaterally paired dimensions of the pelvic canal, non‐canal pelvis, and femur in female (n = 111) and male (n = 126) skeletons from nine geographically dispersed skeletal samples. Directional asymmetries were uniformly low for all measures and lacked any consistent patterning across the variables, while %AA was highest in the pelvic canal, particularly the posterior aspects. Few sex differences and no population differences were found for %DA and %AA; however the latter was correlated with coefficients of variation across the 14 variables in both sexes. While sample mean %DA were low, standard deviations of the canal variables were high and the majority of individuals in both sexes displayed %DA values >±0.5, suggesting asymmetry is common, if not directionally consistent. Biomechanical loading of the pelvic girdle may influence asymmetry of both the canal and non‐canal aspects of the pelvis; however it is unlikely that these asymmetries negatively affect obstetric function, given the prevalence for %DA found in this study. Anat Rec, 300:653–665, 2017. © 2017 Wiley Periodicals, Inc.
The Biomechanical and Energetic Advantages of a Mediolaterally Wide Pelvis in Women
Authors: Wall‐Scheffler Cara M. , Myers Marcella J.
Published: March 2017

Here, we argue that two key shifts in thinking are required to more clearly understand the selection pressures shaping pelvis evolution in female hominins: (1) the primary locomotor mode of female hominins was loaded walking in the company of others, and (2) the periodic gait of human walking is most effectively explained as a biomechanically controlled process related to heel‐strike collisions that is tuned for economy and stability by properly‐timed motor inputs (a model called dynamic walking). In the light of these two frameworks, the evidence supports differences between female and male upper‐pelvic morphology being the result of the unique reproductive role of female hominins, which involved moderately paced, loaded walking in groups. Anat Rec, 300:764–775, 2017. © 2017 Wiley Periodicals, Inc.
Congenital Anatomical Variant of the Clavicle
Authors: Viciano Joan , Urbani Vincenzo , D'Anastasio Ruggero
Published: March 2017

The aim of this study is to present a rare abnormality of the clavicle (Code: SGS01) that was discovered in an ossuary in the Church of San Gaetano (Sulmona, central Italy; XVII–XIX centuries CE). In the middle third, the clavicle had three areas with losses of substance in the form of oval‐shaped foramina with maximum diameters of 1–2 cm that were located in the anterior and superior surfaces of the diaphysis. The margins of these foramina were well defined and rounded, and the surfaces of the canal walls were smooth. Additionally, there were no zones of bony activity or reactive changes around the foramina. This new congenital anomaly of the clavicle and blood vessels is consistent with a variant that might have originated during fetal growth in which the subclavian vein or artery remained included during the process of ossification of the clavicle. Anat Rec, 300:1401–1408, 2017. © 2017 Wiley Periodicals, Inc.
A Comprehensive Study of Palate Development in Miniature Pig
Authors: Sun Lindong , Wang Jiangyi , Liu Huina , Fan Zhipeng , Wang Songlin , Du Juan
Published: March 2017

Palate development is an important morphogenetic event in facial development, including the fusion of the lateral and medial nasal portions of the frontonasal process and maxilla. Derailments of any of these events may result in cleft palate, the most frequent congenital craniofacial abnormality. Recent research has shown that the microanatomy of the miniature pig oral maxillofacial region is quite similar to that of humans, and the use of miniature pigs as a large animal model for dental and orofacial research is increasing. Little information is available, however, about the development of the miniature pig palate. Here, using histological and ultrastructural methods, we describe the developmental stages of the palate in miniature pigs. Sections from E26, E30, E35, E40, E45, and E50 embryos were stained with hematoxylin–eosin, and selected specimens were also processed for electron microscopy. The development of the miniature pig palate can be divided into four stages: growth of the bilateral palatal shelves alongside the tongue at E30; elevation of the horizontal position above the tongue at E35; establishment of bilateral shelf contact at the midline from E35–50; and a final fusion step at E50, similar to the mouse and human. The histological characteristics of the miniature pig palate at different developmental stages were synchronously verified at the ultrastructural level. Our study provides a piece of first‐hand data regarding palate morphological organogenesis in the miniature pig and a foundation for further research with this model to explore mechanisms of cleft palate development. Anat Rec, 300:1409–1419, 2017. © 2017 Wiley Periodicals, Inc.
Studying the effects of emerging infections on the fetus: Experience with West Nile and Zika viruses
Authors: Rasmussen Sonja A. , Meaney‐Delman Dana M. , Petersen Lyle R. , Jamieson Denise J.
Published: March 2017

Emerging infections have the potential to produce adverse effects on the pregnant woman or her fetus; however, studying these effects is often challenging. We review our experiences with investigating the prenatal effects of two mosquito‐borne infections that emerged in the past 2 decades, West Nile virus (WNV) and Zika virus. Concerns regarding teratogenicity were raised about both viruses; Zika virus has been confirmed to be teratogenic, while WNV appears not to increase the risk for adverse outcomes, although teratogenicity has not been excluded. Study designs used to examine the effects of both viruses include case reports and series, pregnancy registries, and cohort studies. Case–control studies and birth defects surveillance systems are being used to study the effects during pregnancy of Zika virus, but not the effects of WNV, because a specific phenotype was observed among infants with congenital Zika infection, but not among infants with congenital WNV infection. Experimental data that demonstrated that Zika virus was neurotropic have also been useful because they provided biologic plausibility for Zika virus's teratogenic effects: these findings were consistent with observations in congenitally infected infants. Challenges encountered with studies to evaluate the effects of these infections include the broad range of possible adverse outcomes, the inability to include all infected pregnant women in studies because many infections are asymptomatic, and the difficulty with interpretation of diagnostic testing of infants (WNV and Zika) and pregnant women (Zika). This review might be helpful to guide future studies of the effects of emerging infections during pregnancy. Birth Defects Research 109:363–371, 2017. © 2017 Wiley Periodicals, Inc.
Ebola virus disease and pregnancy: A review of the current knowledge of Ebola virus pathogenesis, maternal, and neonatal outcomes
Authors: Bebell Lisa M. , Oduyebo Titilope , Riley Laura E.
Published: March 2017

The 2014 to 2016 Ebola virus disease (EVD) outbreak in West Africa devastated local health systems and caused thousands of deaths. Historical reports from Zaire ebolavirus outbreaks suggested pregnancy was associated with an increased risk of severe illness and death, with mortality rates from 74 to 100%. In total, 111 cases of pregnant patients with EVD are reported in the literature, with an aggregate maternal mortality of 86%. Pregnancy‐specific data published from the recent outbreak include four small descriptive cohort studies and five case reports. Despite limitations including reporting bias and small sample size, these studies suggest mortality in pregnant women may be lower than previously reported, with five of 13 (39%) infected women dying. Optimal treatments for pregnant women, and differences in EVD course between pregnant women and nonpregnant individuals, are major scientific gaps that have not yet been systematically addressed. Ebola virus may be transmitted from mother to baby in utero, during delivery, or through contact with maternal body fluids after birth including breast milk. EVD is almost universally fatal to the developing fetus, and limited fetal autopsy data prevent inferences on risk of birth defects. Decisions about delivery mode and other obstetric interventions should be individualized. WHO recommends close monitoring of survivors who later become pregnant, but does not recommend enhanced precautions at subsequent delivery. Although sexual transmission of Ebola virus has been documented, birth outcomes among survivors have not been published and will be important to appropriately counsel women on pregnancy outcomes and inform delivery precautions for healthcare providers. Birth Defects Research 109:353–362, 2017. © 2017 Wiley Periodicals, Inc.
Update on syphilis and pregnancy
Authors: Tsimis Michael E. , Sheffield Jeanne S.
Published: March 2017

While the origins of syphilis remain unknown, it has long been recognized as an infectious entity with complex pathophysiology. In this review, we highlighted the epidemiology and risk factors associated with syphilis. The incidence of syphilis in most populations showed a consistent upward trend until the 1940s with the introduction of penicillin as the preferred treatment. The emergence of congenital syphilis and vertical transmission has been a direct result of heterosexual syphilis transmission. We also explore the microbiology and pathogenesis of Treponema pallidum as it directly correlates with its route of transmission and infectivity. The clinical features are best categorized into stages (primary, secondary, early, and late latent and tertiary). The primary stage presents as a characteristic chancre and inguinal adenopathy, while the secondary “bacteremia” stage has a predilection to dermatologic manifestations and constitutional symptoms. The latent phase of syphilis witnesses a quiescent period with variable relapse of symptoms and finally, one‐third of untreated patients undergo tertiary syphilis years after the initial infection characterized by severe neurologic or cardiovascular symptomatology. We will also review the data collected for congenital syphilis from the CDC as this can manifest with stillbirth, neonatal death, and nonimmune hydrops. The diagnosis of syphilis focuses on a combination of nontreponemal and treponemal antibody tests with the CDC recommending a traditional algorithm from screening to confirmation. However, other agencies have recently adopted the reverse testing algorithm which has outperformed the traditional algorithm in certain populations. We finally focus on syphilotherapy and monitoring response to treatment with a specific emphasis on pregnancy. Birth Defects Research 109:347–352, 2017. © 2017 Wiley Periodicals, Inc.
In situ esterification and extractive fermentation for butyl butyrate production with Clostridium tyrobutyricum
Authors: Zhang Zhong‐Tian , Taylor Steven , Wang Yi
Published: March 2017

Butyl butyrate (BB) is a valuable chemical that can be used as flavor, fragrance, extractant, and so on in various industries. Meanwhile, BB can also be used as a fuel source with excellent compatibility as gasoline, aviation kerosene, and diesel components. The conventional industrial production of BB is highly energy‐consuming and generates various environmental pollutants. Recently, there have been tremendous interests in producing BB from renewable resources through biological routes. In this study, based on the fermentation using the hyper‐butyrate producing strain Clostridium tyrobutyricum ATCC 25755, efficient BB production through in situ esterification was achieved by supplementation of lipase and butanol into the fermentation. Three commercially available lipases were assessed and the one from Candida sp. (recombinant, expressed in Aspergillus niger) was identified with highest catalytic activity for BB production. Various conditions that might affect BB production in the fermentation have been further evaluated, including the extractant type, enzyme loading, agitation, pH, and butanol supplementation strategy. Under the optimized conditions (5.0 g L−1 of enzyme loading, pH at 5.5, butanol kept at 10.0 g L−1), 34.7 g L−1 BB was obtained with complete consumption of 50 g L−1 glucose as the starting substrate. To our best knowledge, the BB production achieved in this study is the highest among the ever reported from the batch fermentation process. Our results demonstrated an excellent biological platform for renewable BB production from low‐value carbon sources. Biotechnol. Bioeng. 2017;114: 1428–1437. © 2017 Wiley Periodicals, Inc.
Evaluation of two public genome references for chinese hamster ovary cells in the context of rna‐seq based gene expression analysis
Authors: Chen Chun , Le Huong , Goudar Chetan T.
Published: March 2017

RNA‐Seq is a powerful transcriptomics tool for mammalian cell culture process development. Successful RNA‐Seq data analysis requires a high quality reference for read mapping and gene expression quantification. Currently, there are two public genome references for Chinese hamster ovary (CHO) cells, the predominant mammalian cell line in the biopharmaceutical industry. In this study, we compared these two references by analyzing 60 RNA‐Seq samples from a variety of CHO cell culture conditions. Among the 20,891 common genes in both references, we observed that 31.5% have more than 7.1% quantification differences, implying gene definition differences in the two references. We propose a framework to quantify this difference using two metrics, Consistency and Stringency, which account for the average quantification difference between the two references over all samples, and the sample‐specific effect on the quantification result, respectively. These two metrics can be used to identify potential genes for future gene model improvement and to understand the reliability of differentially expressed genes identified by RNA‐Seq data analysis. Before a more comprehensive genome reference for CHO cells emerges, the strategy proposed in this study can enable more robust transcriptome analysis from CHO cell RNA‐Seq data. Biotechnol. Bioeng. 2017;114: 1603–1613. © 2017 Wiley Periodicals, Inc.
A novel sugar analog enhances sialic acid production and biotherapeutic sialylation in CHO cells
Authors: Yin Bojiao , Wang Qiong , Chung Cheng‐Yu , Bhattacharya Rahul , Ren Xiaozhi , Tang Juechun , Yarema Kevin J. , Betenbaugh Michael J.
Published: March 2017

A desirable feature of many therapeutic glycoprotein production processes is to maximize the final sialic acid content. In this study, the effect of applying a novel chemical analog of the sialic acid precursor N‐acetylmannosamine (ManNAc) on the sialic acid content of cellular proteins and a model recombinant glycoprotein, erythropoietin (EPO), was investigated in CHO‐K1 cells. By introducing the 1,3,4‐O‐Bu3ManNAc analog at 200–300 µM into cell culture media, the intracellular sialic acid content of EPO‐expressing cells increased ∼8‐fold over untreated controls while the level of cellular sialylated glycoconjugates increased significantly as well. For example, addition of 200–300 µM 1,3,4‐O‐Bu3ManNAc resulted in >40% increase in final sialic acid content of recombinant EPO, while natural ManNAc at ∼100 times higher concentration of 20 mM produced a less profound change in EPO sialylation. Collectively, these results indicate that butyrate‐derivatization of ManNAc improves the capacity of cells to incorporate exogenous ManNAc into the sialic acid biosynthetic pathway and thereby increase sialylation of recombinant EPO and other glycoproteins. This study establishes 1,3,4‐O‐Bu3ManNAc as a novel chemical supplement to improve glycoprotein quality and sialylation levels at concentrations orders of magnitude lower than alternative approaches. Biotechnol. Bioeng. 2017;114: 1899–1902. © 2017 Wiley Periodicals, Inc.
Matrine regulates Th1/Th2 cytokine responses in rheumatoid arthritis by attenuating the NF‐κB signaling
Authors: Niu Yaojie , Dong Qiumei , Li Rongheng
Published: March 2017

To investigate the efficacy and mechanisms of matrine, a component derived from Sophora flavescens in treatment of rheumatoid arthritis (RA), a rat model of RA was established. Compared to control rats, matrine significantly mitigated inflammation and severity of RA (paw volume and articular index (AI) score). Using either mice splenic T cells stimulated with PMA/ionomycin or rat splenic T cells, the levels of Th1 and Th2 responses were determined by flow cytometry, quantitative RT‐PCR, and ELISA. Furthermore, the levels of NF‐κBp65 (RelA), IκBα, and phosphor‐IκBα in T cells were determined by Western blot. Our study found that matrine modulated the imbalance of Th1 and Th2 cytokine responses in rats with RA by reducing the levels of Th1 cytokines (IFN‐γ, TNF‐α, IL‐1β), but increasing Th2 cytokine (IL‐4 and IL‐10) through attenuating the NF‐κB signaling in T cells, suggesting matrine as a promising drug for intervention of RA.
Bioprosthetic mitral valve paravalvular leak closure using intracardiac echocardiography‐guided three dimensional electroanatomic mapping
Authors: Al'Aref Subhi J. , Devereux Richard B. , Cheung Jim W. , Bergman Geoffrey
Published: March 2017

The development of paravalvular leak (PVL) following surgical replacement of an aortic or mitral valve is an uncommon complication with significant morbidity and mortality. Surgical or percutaneous repair of PVL can be technically challenging. We describe the application of intracardiac echocardiography guided 3‐dimensional electroanatomic mapping to facilitate PVL closure in a symptomatic patient with a previously placed bioprosthetic mitral valve. © 2017 Wiley Periodicals, Inc.
Incidence and predictors of early and late target lesion revascularization after everolimus‐eluting stent implantation in unselected patients in japan
Authors: Kurihara Ken , Ashikaga Takashi , Sasaoka Taro , Yoshikawa Shunji , Isobe Mitsuaki ,   Tokyo‐MD PCI Study Investigators
Published: March 2017

Objective

The objective of this study was to clarify the incidence and predictors of early and late target lesion revascularization (TLR) after everolimus‐eluting stent (EES) implantation in actual clinical practice.

Background

Several clinical studies have reported the incidence and predictors of TLR after EES implantation. However, detailed features of early and late TLR are unknown.

Methods

We analyzed the clinical data of patients who underwent EES implantation between January 2010 and December 2011 at 22 institutions in Japan (Tokyo‐MD PCI study). Patients who underwent ischemia‐driven TLR (ID‐TLR) were grouped according to the number of years elapsed since stent placement, and incidence and correlations between clinical factors were analyzed.

Results

Statistical analysis was performed for 1,899 patients and 2,305 lesions. The mean age was 70.0 ± 9.9 years, and the median follow‐up period was 1,281 days (IQR: 762–1,440 days). The incidence of ID‐TLR was 2.7% at 1 year and 5.4% at 4 years. After 2 years, the ID‐TLR rates plateaued. The independent predictors of ID‐TLR occurring within 2 years were hemodialysis, triple vessel disease, restenotic lesion, and ostial lesions. The independent predictors of ID‐TLR between 2 and 4 years were diabetes mellitus and peripheral artery disease.

Conclusion

The ID‐TLR rates leveled off after 2 years. Furthermore, the predictors of ID‐TLR that occurred within 2 years of EES implantation differed from those that occurred later than 2 years. © 2017 Wiley Periodicals, Inc.
Role of residual acute stent malapposition in percutaneous coronary interventions
Authors: Romagnoli Enrico , Gatto Laura , La Manna Alessio , Burzotta Francesco , Taglieri Nevio , Saia Francesco , Amico Francesco , Marco Valeria , Ramazzotti Vito , Di Giorgio Alessandro , Di Vito Luca , Boi Alberto , Contarini Marco , Castriota Fausto , Mintz Gary S. , Prati Francesco
Published: March 2017

Objectives

Assess clinical consequences of acute stent malapposition (ASM) in the context of the multicenter Centro per la Lotta Contro l'Infarto‐Optimization of Percutaneous Coronary Intervention (CLI‐OPCI) registry.

Background

ASM as important determinant of stent thrombosis (ST) risk remains controversial.

Methods

From 2009 to 2013, we retrospectively analyzed postprocedural optical coherence tomography (OCT) findings in 864 patients undergoing percutaneous coronary intervention, assessing prevalence and magnitude of ASM and exploring correlation with outcome, especially ST.

Results

Postprocedural OCT revealed a variable grade of ASM in 72.3% of stents without correlation between maximal strut‐vessel distance and longitudinal extension (R = 0.164, P < 0.01). At a median follow up of 302 (IQ 127–567) days, ASM did not affect risk of following major cardiac adverse events (MACE); residual ASM was comparable in terms of thickness (median [quartiles] 0.21[IQ 0.1–0.4] vs. 0.20[IQ 0.0–0.3], P = 0.397) and length (2.0[IQ 0.5–4.1] vs. 2.2[IQ 0.0–5.2], P = 0.640) in patients with versus without MACE. The predictive accuracy for outcome was low (C‐statistic 0.52, CI 95% 0.47–0.58, P = 0.394) as well for target lesion revascularization (HR 0.80, CI 95% 0.5–1.4) and ST (HR 0.71, CI 95% 0.3–1.5). Likewise, timing to MACE was not influenced by presence of such an ASM with similar rate of acute‐subacute (HR 1.09, CI 95% 0.6–1.9), late (HR 0.91, CI 95% 0.5–1.8), and very late (HR 1.23, CI 95% 0.5–2.9) events.

Conclusions

Limited ASM was a common finding after stent implantation, but was not associated to increased risk of stent failure or ST during mid‐term follow‐up. © 2017 Wiley Periodicals, Inc.
Direct percutaneous transaxillary implantation of a novel self‐expandable transcatheter heart valve for aortic stenosis
Authors: Deuschl Florian , Schofer Niklas , Seiffert Moritz , Hakmi Samer , Mizote Isamu , Schaefer Andreas , Schirmer Johannes , Reichenspurner Hermann , Blankenberg Stefan , Conradi Lenard , Schäfer Ulrich
Published: March 2017

Objectives

The aim of this study was to evaluate safety, feasibility, and efficacy of transaxillary TAVI using a novel self‐expandable transcatheter heart valve (THV) via a direct percutaneous technique.

Methods

The analysis comprises 12 consecutive patients with severe aortic stenosis treated with the ACURATE Neo™ THV (Symetis) by direct percutaneous transaxillary access.

Results

Patients presented with a mean age of 79.9 ± 6.2 years and high calculated surgical risk (logEuroSCORE I: 19.55 ± 15.00%; STS PROM score: 5.42 ± 3.25%). Transaxillary TAVI was performed in 11/12 via the left and in 1/12 via the right‐sided axillary artery. Device success was achieved in all patients (12/12). Mortality rate at 30 days was 0% (0/12). No major and one minor access site complication (1/12) occurred. No major or life‐threatening access site‐related bleeding resulted. None of the patients suffered from postprocedural stroke/transient ischemic attack. There was no need for a permanent pacemaker. Mean effective orifice area post implantation was 2.1 ± 0.29 cm2 and mean aortic gradient 6.2 ± 1.5 mm Hg. In none of the patients, greater than moderate aortic regurgitation or paravalvular leakage was detected at discharge (0/12).

Conclusions

Our study suggests that the implantation of the second‐generation self‐expandable ACURATE Neo™ via a transaxillary access is technically feasible and safe and yields excellent short‐term clinical results. © 2017 Wiley Periodicals, Inc.
Emergency valve‐in‐valve transcatheter aortic valve replacement in a patient with degenerated bioprosthetic aortic stenosis and cardiogenic shock on veno‐arterial extracorporeal membrane oxygenation
Authors: Summers Matthew R. , Mick Stephanie , Kapadia Samir R. , Krishnaswamy Amar
Published: March 2017

The use of transcatheter aortic valve replacement (TAVR) as an acute treatment in severe decompensated bioprosthetic aortic valve disease is not well documented. We describe herein a unique case in which valve‐in‐valve (ViV) TAVR was successfully used as both an emergency salvage therapy and a bridge to definitive fourth reoperative aortic valve replacement (AVR) in a young patient with cardiogenic shock secondary to bioprosthetic aortic valve stenosis who was dependent on veno‐arterial extracorporeal membrane oxygenation (VA‐ECMO). © 2017 Wiley Periodicals, Inc.
Transcatheter closure of unroofed coronary sinus using covered stents in an adult with drainage of the coronary sinus to the right ventricle after supra‐annular tricuspid valve replacement
Authors: Mohammad Nijres Bassel , Kenny Damien , Kazmouz Suhaib , Hijazi Ziyad M.
Published: March 2017

We present a rare case of unroofed coronary sinus in a patient who underwent supra‐annular tricuspid valve replacement with consequent drainage of the coronary sinus to the right ventricle. It is unclear whether the coronary sinus was unroofed congenitally or iatrogenically. This rare setup resulted in significant cyanosis. The abnormal drainage was successfully closed via trans‐catheter delivery of covered stents with resolution of the cyanosis. © 2017 Wiley Periodicals, Inc.
Accurate Bond Lengths to Hydrogen Atoms from Single‐Crystal X‐ray Diffraction by Including Estimated Hydrogen ADPs and Comparison to Neutron and QM/MM Benchmarks
Authors: Dittrich Birger , Lübben Jens , Mebs Stefan , Wagner Armin , Luger Peter , Flaig Ralf
Published: March 2017

Amino acid structures are an ideal test set for method‐development studies in crystallography. High‐resolution X‐ray diffraction data for eight previously studied genetically encoding amino acids are provided, complemented by a non‐standard amino acid. Structures were re‐investigated to study a widely applicable treatment that permits accurate X−H bond lengths to hydrogen atoms to be obtained: this treatment combines refinement of positional hydrogen‐atom parameters with aspherical scattering factors with constrained “TLS+INV” estimated hydrogen anisotropic displacement parameters (H‐ADPs). Tabulated invariom scattering factors allow rapid modeling without further computations, and unconstrained Hirshfeld atom refinement provides a computationally demanding alternative when database entries are missing. Both should incorporate estimated H‐ADPs, as free refinement frequently leads to over‐parameterization and non‐positive definite H‐ADPs irrespective of the aspherical scattering model used. Using estimated H‐ADPs, both methods yield accurate and precise X−H distances in best quantitative agreement with neutron diffraction data (available for five of the test‐set molecules). This work thus solves the last remaining problem to obtain such results more frequently. Density functional theoretical QM/MM computations are able to play the role of an alternative benchmark to neutron diffraction.
Near‐Infrared Photoinduced Reactions Assisted by Upconverting Nanoparticles
Authors: Wu Si , Blinco James P. , Barner‐Kowollik Christopher
Published: March 2017

The majority of photoreactions reported in the literature rely on wavelengths within the UV and—to a lesser extent—visible regime for activation, either by directly triggering the reaction or by photocatalysis. However, photoreactions induced by near‐infrared (NIR) light are highly attractive for biomedical applications as NIR light can penetrate deeper into tissue and causes less damage to photosensitive biological systems. Recently, upconverting nanoparticles (UCNPs) have been employed by us and others to assist NIR photoinduced reactions. UCNPs convert NIR light to UV or visible light, which can trigger photoreactions of conventional UV or visible‐light‐sensitive compounds. In the current Concept article, we introduce the fundamentals of UCNP‐assisted photochemistry and highlight selected future applications and innovative potential for the field.