bluuebunny/crossref_metadata_2025 huggingface dataset:
Strategic Advances in Formation of Cell‐in‐Shell Structures: From Syntheses to Applications
Authors: Kim Beom Jin , Cho Hyeoncheol , Park Ji Hun , Mano João F. , Choi Insung S.
Published: February 2018

Single‐cell nanoencapsulation, forming cell‐in‐shell structures, provides chemical tools for endowing living cells, in a programmed fashion, with exogenous properties that are neither innate nor naturally achievable, such as cascade organic‐catalysis, UV filtration, immunogenic shielding, and enhanced tolerance in vitro against lethal factors in real‐life settings. Recent advances in the field make it possible to further fine‐tune the physicochemical properties of the artificial shells encasing individual living cells, including on‐demand degradability and reconfigurability. Many different materials, other than polyelectrolytes, have been utilized as a cell‐coating material with proper choice of synthetic strategies to broaden the potential applications of cell‐in‐shell structures to whole‐cell catalysis and sensors, cell therapy, tissue engineering, probiotics packaging, and others. In addition to the conventional “one‐time‐only” chemical formation of cytoprotective, durable shells, an approach of autonomous, dynamic shellation has also recently been attempted to mimic the naturally occurring sporulation process and to make the artificial shell actively responsive and dynamic. Here, the recent development of synthetic strategies for formation of cell‐in‐shell structures along with the advanced shell properties acquired is reviewed. Demonstrated applications, such as whole‐cell biocatalysis and cell therapy, are discussed, followed by perspectives on the field of single‐cell nanoencapsulation.
Broadband Photodetectors Enabled by Localized Surface Plasmonic Resonance in Doped Iron Pyrite Nanocrystals
Authors: Gong Maogang , Sakidja Ridwan , Liu Qingfeng , Goul Ryan , Ewing Dan , Casper Matthew , Stramel Alex , Elliot Alan , Wu Judy Z.
Published: February 2018

The emerging capability to detect light over a broad spectral range is a key to technological applications in sensing, spectroscopy, imaging and communications. Colloidal semiconductor nanocrystal/graphene van der Waals heterojunctions provide a unique scheme that combines the spectral tunability and strong quantum confinement of the semiconductor nanocrystals sensitizers with superior charge mobility of graphene for extraordinary photoconductive gains. While high responsivity has been demonstrated, the spectral range is typically narrow limited by the cutoff of the semiconductor band gap of the nanocrystals. Here, a broadband photosensitizer is reported, based on doped Iron Pyrite nanocubes (FeS2 NCs) that exhibit strong localized surface plasmonic resonance (LSPR) spanning across ultraviolet through visible to near‐infrared (UV–Vis–NIR). Using the printed LSPR FeS2 NCs/graphene van der Waals heterostructure, a broadband UV–Vis–NIR photoresponsivity in exceeding 1.08 × 106 A/W has been demonstrated through development of a ligand‐exchange process to facilitate efficient charge transfer at the LSPR FeS2 NCs/graphene interface. This result demonstrates the viability of the LSPR semiconductor nanocrystal/graphene van der Waals heterostructure for high‐performance broadband optoelectronics with scalability through direct printing.
A Novel and Versatile Grafting Procedure: Toward the Highest Possible Sulfonation Degree of Mesoporous Silica
Authors: Timm Jana , Marschall Roland
Published: February 2018

A unique method for the postsynthetic functionalization of ordered mesoporous silica materials is described. The functionalization is done via a chemical vapor deposition‐type method and leads to the quantitative reaction of isolated surface silanol groups of mesoporous silica materials with organosilane molecules. The result is a highly sulfonated material by anchorage of 3‐mercaptopropyltrimethoxysilane molecules and subsequent oxidation of the thiol groups to sulfonic acid groups. Ordered mesoporous KIT‐6 and SBA‐15 are chosen as model systems. The sulfonated material exhibits a functionalization degree of 1.05 resp. 1.32 molecules nm−2, which is on the maximum of the theoretical achievable functionalization density resulting in high ion exchange capacities of 1.22 and 1.12 mmol g−1. The versatility and mildness of this method opens up functionalization possibilities for a wide range of other materials, which could be sulfonated or otherwise modified with silanes, and tailored for the further application in catalysis or as solid‐state proton conductors.
Solvothermal‐Derived S‐Doped Graphene as an Anode Material for Sodium‐Ion Batteries
Authors: Quan Bo , Jin Aihua , Yu Seung‐Ho , Kang Seok Mun , Jeong Juwon , Abruña Héctor D. , Jin Longyi , Piao Yuanzhe , Sung Yung‐Eun
Published: February 2018

Sodium‐ion batteries (SIBs) have attracted enormous attention in recent years due to the high abundance and low cost of sodium. However, in contrast to lithium‐ion batteries, conventional graphite is unsuitable for SIB anodes because it is much more difficult to intercolate the larger Na ions into graphite layers. Therefore, it is critical to develop new anode materials for SIBs for practical use. Here, heteroatom‐doped graphene with high doping levels and disordered structures is prepared using a simple and economical thermal process. The solvothermal‐derived graphene shows excellent performance as an anode material for SIBs. It exhibits a high reversible capacity of 380 mAh g−1 after 300 cycles at 100 mA g−1, excellent rate performance 217 mAh g−1 at 3200 mA g−1, and superior cycling performance at 2.0 A g−1 during 1000 cycles with negligible capacity fade.
The Crystallization of Amorphous Calcium Carbonate is Kinetically Governed by Ion Impurities and Water
Authors: Albéric Marie , Bertinetti Luca , Zou Zhaoyong , Fratzl Peter , Habraken Wouter , Politi Yael
Published: February 2018

Many organisms use amorphous calcium carbonate (ACC) and control its stability by various additives and water; however, the underlying mechanisms are yet unclear. Here, the effect of water and inorganic additives commonly found in biology on the dynamics of the structure of ACC during crystallization and on the energetics of this process is studied. Total X‐ray scattering and pair distribution function analysis show that the short‐ and medium‐range order of all studied ACC samples are similar; however, the use of in situ methodologies allow the observation of small structural modifications that are otherwise easily overlooked. Isothermal calorimetric coupled with microgravimetric measurements show that the presence of Mg2+ and of PO43− in ACC retards the crystallization whereas increased water content accelerates the transformation. The enthalpy of ACC with respect to calcite appears, however, independent of the additive concentration but decreases with water content. Surprisingly, the enthalpic contribution of water is compensated for by an equal and opposite entropic term leading to a net independence of ACC thermodynamic stability on its hydration level. Together, these results point toward a kinetic stabilization effect of inorganic additives and water, and may contribute to the understanding of the biological control of mineral stability.
A Material Perspective of Rechargeable Metallic Lithium Anodes
Authors: Li Bin , Wang Ying , Yang Shubin
Published: February 2018

Rechargeable lithium‐based batteries are long considered as the most promising candidates for application in various electronic devices, electric vehicles, and even electrical grids owing to their ultrahigh energy densities. However, to date, metallic lithium‐based batteries are still far from practical applications due to the low Coulombic efficiency and fast capacity decay of lithium anodes. The poor electrochemical performances of metallic lithium anodes are inherently related to random growth of lithium dendrites and infinite volume charge of lithium anodes. In this review, the failure mechanisms of metallic lithium anodes are summarized and ascribed to the unstable and inhomogeneous solid electrolyte interphase, uneven distributions of electric field, and lithium‐ion flux during the lithium plating processes. Correspondingly, efficient strategies for mitigating these problems, including surficial engineering, electric field, and lithium‐ion flux regulation are discussed from the perspective of anode materials. Finally, an outlook is proposed for the design and fabrication of next‐generation rechargeable metallic lithium anodes that aims to address the intrinsic problems of metallic lithium anodes.
Hydrodynamics in a pilot‐scale cocurrent trickle‐bed reactor at low gas velocities
Authors: Kawatra Puneet , Panyaram Srikanth , Wilhite Benjamin A.
Published: February 2018

Hydrodynamic data obtained from laboratory‐scale trickle‐beds often fail to accurately represent industrial‐scale systems with high packing aspect ratios and column‐to‐particle diameter ratios. In this study, pressure drop, liquid holdup, and flow regime transition were investigated in a pilot‐scale trickle‐bed column of 33 cm ID and 2.45 m bed height packed with 1.6 mm × 8.4 ± 1.4 mm cylindrical extrudates for air‐water mass superficial velocities of 0.0023 – 0.094 kg/m2s and 4.5 – 45 kg/m2s, respectively, at atmospheric pressure. Significant deviation was observed from pressure drop and liquid holdup correlations at low liquid flows rates, corresponding to gravity‐driven flow limit. Likewise, liquid saturation is overestimated by correlations at high liquid flow rates, owing to significantly reduced wall effects. Lastly, trickle‐to‐dispersed bubble flow and trickle‐to‐pulsing flow regime transitions are reported using a combination of visual observations and analysis of the magnitude of local pressure fluctuations within the column. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2560–2569, 2018
Experimental data for code validation: Horizontal air jets in a semicircular fluidized bed of Geldart Group D particles
Authors: Fullmer William D. , LaMarche Casey Q. , Issangya Allan , Liu Peiyuan , Cocco Ray , Hrenya Christine M.
Published: February 2018

Experiments were conducted with 6 mm plastic beads (Geldart Group D) in a semi‐circular, gas‐fluidized bed with side jets. Attention was paid to particle characterization and bed measurements, making the resulting dataset ideal for CFD‐DEM validation and uncertainty quantification. The bed was operated slightly above and below the minimum fluidization velocity, with additional fluidization provided by one of two pairs of opposing jets located above the distributor near the flat, front face of the unit. Care is taken to report material properties and bed conditions with either measured distribution functions or uncertainty bounds. High‐speed video imaging and particle tracking velocimetry are used to extract bin‐averaged velocity profiles, which are used to extract jet penetration depths. The time‐averaged mean and standard deviation of the bed pressure drop is also reported. Finally, the lower jets are also inserted into the bed until the opposing jets merge to form a spout‐like pattern. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2351–2363, 2018
New prospects in the detection and comparative analysis of hybridization in the tree of life
Authors: Folk Ryan A. , Soltis Pamela S. , Soltis Douglas E. , Guralnick Robert
Published: February 2018

Assessing the relative importance of the various pathways to diversification is a central goal of biodiversity researchers. For plant biologists, and increasingly across the spectrum of biological sciences, among these pathways of interest is hybridization. New methodological developments are moving the field away from questions of whether natural hybridization occurs or hybrids can persist and toward more direct assessments of the long‐term impact of hybridization on diversification and genome organization. Advances in theory and new data, especially phylogenomic data, have changed the face of this field, revealing extensive occurrences of hybridization at both shallow and deep levels, but lacking is a synthesis of these advancements. Here we provide an overview of methods that have been proposed for detecting hybridization with molecular data and advocate a time‐extended, comparative view of reticulate evolution. In particular, we pose three overarching questions, newly placed within reach, that are critical for advancing our understanding of hybridization pattern and process: (1) How often is introgression biased toward certain genomes and loci, and is this bias selectively neutral? (2) What are the relative rates of formation of hybrid species and introgressants, and how does this compare to their subsequent fates? (3) Has the frequency of hybridization increased under historical periods of greater dynamism in climate and geographic range, such as the Pleistocene?
The clinical implications of adopting new criteria for the grading of internal carotid artery stenosis
Authors: Curtis Nicole , Necas Martin , Versteeg Matthew
Published: February 2018

Introduction

A patient's eligibility for carotid endarterectomy (CEA) is determined primarily by the degree of carotid stenosis detected on duplex ultrasound. The Australasian Society for Ultrasound in Medicine (ASUM) criteria are widely used to grade carotid stenoses in many practices throughout Australasia.

Methods

We sought to investigate the potential impact on the grading of carotid artery stenosis if practitioners switched from the ASUM criteria to the United Kingdom's joint recommendation (UKJR) criteria by reviewing 100 patients with a haemodynamically significant carotid artery stenosis.

Results

We found agreement between the criteria in 100% of cases for stenoses <50%, in 80% of cases for stenoses 50–69%, in 89% of cases for stenoses ≥70% and in 100% of cases for stenoses ≥80%. While there was variation in grading of stenoses in 16% of cases, reclassification resulted in no change in the number of patients eligible for CEA. The UKJR guideline enabled more precise categorisation of haemodynamically significant stenosis into deciles.

Discussion

Because the UKJR guideline is more comprehensive, we believe that adopting this guideline would enable the ultrasound practitioner to grade carotid stenoses more precisely, better understand the nuances of carotid duplex imaging and more successfully navigate and interpret complex carotid examinations, without impacting the number of patients eligible for CEA.
Towards Sequence‐Controlled Antimicrobial Polymers: Effect of Polymer Block Order on Antimicrobial Activity
Authors: Judzewitsch Peter R. , Nguyen Thuy‐Khanh , Shanmugam Sivaprakash , Wong Edgar H. H. , Boyer Cyrille
Published: February 2018

Synthetic polymers have shown promise in combating multidrug‐resistant bacteria. However, the biological effects of sequence control in synthetic antimicrobial polymers are currently not well understood. As such, we investigate the antimicrobial effects of monomer distribution within linear high‐order quasi‐block copolymers consisting of aminoethyl, phenylethyl, and hydroxyethyl acrylamides made in a one‐pot synthesis approach via photoinduced electron transfer–reversible addition–fragmentation chain transfer polymerisation (PET‐RAFT). Through different combinations of monomer/polymer block order, antimicrobial and haemolytic activities are tuneable in a manner comparable to antimicrobial peptides.
Chemoselective Synthesis of Z‐Olefins through Rh‐Catalyzed Formate‐Mediated 1,6‐Reduction
Authors: Dada Raphael , Wei Zhongyu , Gui Ruohua , Lundgren Rylan J.
Published: February 2018

Z‐olefins are important functional units in synthetic chemistry; their preparation has thus received considerable attention. Many prevailing methods for cis‐olefination are complicated by the presence of multiple unsaturated units or electrophilic functional groups. In this study, Z‐olefins are delivered through selective reduction of activated dienes using formic acid. The reaction proceeds with high regio‐ and stereoselectivity (typically >90:10 and >95:5, respectively) and preserves other alkenyl, alkynyl, protic, and electrophilic groups.
Shape‐Tunable Colloids from Structured Liquid Droplet Templates
Authors: Luo Zhang , Liu Bing
Published: February 2018

Shaping colloidal building units is of paramount importance for their self‐assembly into complex objects. Continuous tuning of colloidal shapes is highly desired for understanding self‐assembly, but it still remains a challenge. Herein, we report a new template strategy for the shape‐tunable synthesis of anisotropic colloids with shapes that can be continuously tuned from discs (oblate spheroids) to spheres to theta shapes to dumbbells. This was realized by creating structured shape‐tunable droplets from patchy colloidal discs and using these droplets as templates. In particular, we found that a controlled dumbbell‐to‐eyeball droplet transformation can be used for the synthesis of eyeball‐shaped colloids. We also demonstrated the droplet transformation pathways and applied the method to the synthesis of colloidal molecules. These colloids provide possibilities for exploring their ordered packing structures, and the method based on the use of structured droplets can be adapted for the synthesis of other functional colloidal particles.
Antibacterial poly{(4‐vinyl phenylboronic acid)‐co‐[2‐(dimethylamino)ethyl methacrylate]} copolymers and their application in water‐based paints
Authors: Cicek Hüseyin , Kocak Gökhan , Ceylan Özgür , Kutluca Emir Ahmet , Dikmen Zeynep , Bütün Vural
Published: February 2018

Herein, we report the synthesis of poly(4‐vinylphenylboronic acid) (PVPBA) and poly[2‐(dimethylamino)ethyl methacrylate] (PDMAEMA) homopolymers, copolymers, and their methyl, pentyl, and octyl quaternized forms as dopant in water‐based permanent antibacterial paints. Both quaternized and nonquaternized forms of P(VPBA‐co‐DMAEMA) copolymers have reflected higher MIC values relative to PDMAEMA homopolymers. High molecular weight copolymers were more active against Escherichia coli ATCC 25922, contrarily, lower molecular weight copolymers showed higher antibacterial activity against Staphylococcus aureus ATCC 25923. The paint films prepared with quaternized PDMAEMA homopolymers with a weight of 10% showed better antibacterial activity in water and airborne tests than the copolymers. However, it has been shown that the inadequate anti‐biofilm properties of homopolymer‐containing paint films are overcome with the VPBA content of the copolymer structure and the most effective antibacterial and anti‐biofilm properties have been obtained with paint films containing P(VPBA‐co‐5QDMAEMA) copolymers. These paint films, which can maintain antibacterial and anti‐biofilm properties for at least 1 year, have the potential to be an alternative to Ag/Cl based solid surfaces which require the active substance to be regenerated. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46245.
How Does China–Pakistan Economic Corridor Show the Limitations of China's ‘One Belt One Road’ Model
Authors: Shah Abdur Rehman
Published: February 2018

Under ‘One Belt One Road’ initiative, China has introduced a new model of economic development of cross‐continental connectivity. With all its promising prospects, the initiative raises a question how such grand designs are going to impact the institutions of countries susceptible to potentially adverse impacts of Chinese investments. The case study of Pakistan — the closest ally of China — is a good example. China has started investing more than $50 billion in energy, industrial and communication infrastructure across the country. But the combination of too much and too quick Chinese investments — free of ‘governance‐related conditionalities’ normally attached with Western aid — and Pakistan's domestic issues has some adverse impacts on latter's internal politics and state institutions. Lack of transparency, civil‐military divide, ethnic differences, discrediting media, widening current account deficit, securitisation of trade and undoing the economic reforms (undertaken under International Monetary Fund program) are some of the unfavourable aspects of China–Pakistan Economic Corridor.
Anatomy integration: Effective change or change of affect?
Authors: Hartley Rebecca S. , Smith Gary A. , Rosenberg Martina J.
Published: February 2018

Anatomy is fundamental to clinical practice, is considered a rite of passage in becoming a physician and is key to professional identity formation. The anatomy course that began the medical curriculum at the University of New Mexico School of Medicine was recently dissolved to address content and process gaps in the pre‐clinical curriculum. Anatomy was integrated into the organ system blocks to make room for new courses to address content gaps. Previous reports of anatomy integration document more positive attitudes and perceptions to teaching anatomy in context, as compared to an independent course. The current prospective study compared two medical student cohorts to determine the effects of teaching anatomy in and out of context on the cognitive and affective domains of learning. In a pre, post, and follow‐up design, methods included content assessments, confidence probes, and attitude surveys informed by focus groups. Results indicated that anatomical knowledge and student confidence was gained and mastered in both curricula. Initial acquisition of content was higher in the integrated curriculum, but not maintained. Students in the integrated curriculum displayed a different relationship to learning anatomy, appearing more concerned with their personal progression than with the connection of anatomy to medical practice or patient care. These students also agreed less with statements related to working in teams, reflective practices and professional identity formation. Further studies will determine if this difference will diminish with continued exposure to anatomy and may inform future curricular adjustments. Anat Sci Educ. © 2018 American Association of Anatomists.
Experimental Studies on the Classification of Airborne Particles Based on Their Optical Properties
Authors: Choi Kibong , Koh Young Jin , Jeong Young‐Su , Chong Eugene
Published: February 2018

We evaluated the proposed correlation value for the analysis of airborne particles using light‐scattering signals and aerodynamic size determined using a well‐known commercial instrument. This method enables the real‐time classification of the components of airborne particles. The correlation value can be applied to classify biological and heavy metal components based on their density. This study opens the path to enhance the current bioaerosol and non‐bioaerosol detection system and could help in optimizing the fast detection and classification of airborne particle components.
Long‐term outcomes of proton therapy for prostate cancer in Japan: a multi‐institutional survey of the Japanese Radiation Oncology Study Group
Authors: Iwata Hiromitsu , Ishikawa Hitoshi , Takagi Masaru , Okimoto Tomoaki , Murayama Sigeyuki , Akimoto Tetsuo , Wada Hitoshi , Arimura Takeshi , Sato Yoshitaka , Araya Masayuki , Mizoe Jun‐etsu , Gosho Masahiko , Nakamura Katsumasa , Shirato Hiroki , Sakurai Hideyuki
Published: February 2018

This is the first multi‐institutional retrospective survey of the long‐term outcomes of proton therapy (PT) for prostate cancer in Japan. This retrospective analysis comprised prostate cancer patients treated with PT at seven centers between January 2008 and December 2011 and was approved by each Institutional Review Board. The NCCN classification was used. Biochemical relapse was based on the Phoenix definition (nadir + 2.0 ng/mL). Toxicities were evaluated with the Common Terminology Criteria for Adverse Events version 4.0. There were 215, 520, and 556 patients in the low‐risk, intermediate‐risk, and high‐risk groups, respectively. The median follow‐up period of surviving patients was 69 months (range: 7–107). Among all patients, 98.8% were treated using a conventional fractionation schedule and 1.2% with a hypofractionation schedule; 58.5% and 21.5% received neoadjuvant and adjuvant androgen deprivation therapy, respectively. The 5‐year biochemical relapse‐free survival (bRFS) and overall survival rates in the low‐risk, intermediate‐risk, and high‐risk groups were 97.0%, 91.1%, and 83.1%, and 98.4%, 96.8%, and 95.2%, respectively. In the multivariate analysis, the NCCN classification was a significant prognostic factor for bRFS, but not overall survival. The incidence rates of grade 2 or more severe late gastrointestinal and genitourinary toxicities were 4.1% and 4.0%, retrospectively. This retrospective analysis of a multi‐institutional survey suggested that PT is effective and well‐tolerated for prostate cancer. Based on this result, a multi‐institutional prospective clinical trial (UMIN000025453) on PT for prostate cancer has just been initiated in order to define its role in Japan.
PRMT5 promotes cell proliferation by inhibiting BTG2 expression via the ERK signaling pathway in hepatocellular carcinoma
Authors: Jiang Hai , Zhu Yue , Zhou Zhenyu , Xu Junyang , Jin Shaowen , Xu Kang , Zhang Heyun , Sun Qing , Wang Jie , Xu Junyao
Published: February 2018

Increasing evidence suggests that PRMT5, a protein arginine methyltransferase, has roles in cell growth regulation and cancer development. However, the role of PRMT5 in hepatocellular carcinoma (HCC) progression remains unclear. Here, we showed that PRMT5 expression was frequently upregulated in HCC tissues, and its expression was inversely correlated with overall survival in HCC patients. PRMT5 knockdown markedly inhibited in vitro HCC proliferation and in vivo tumorigenesis. We revealed that the mechanism of PRMT5‐induced proliferation was partially mediated by BTG downregulation, leading to cell cycle arrest during the G1 phase in HCC cells. Ectopic BTG2 overexpression decreased HCC growth, caused cell cycle arrest at the G1 phase, and downregulated Cyclin D1 and Cyclin E1 protein expression. Furthermore, we found that PRMT5‐induced ERK phosphorylation regulated BTG2 expression in HCC cells, whereas pretreatment with a selective ERK1/2 inhibitor (PD184352) significantly reversed the effect of PRMT5 on BTG2 expression. Our results indicated that PRMT5 promotes HCC proliferation by downregulating BTG2 expression via the ERK pathway.
Milk fistula following puerperal breast abscess
Authors: Lim Geok Hoon , Ng Ruey Pyng
Published: February 2018

Key Clinical Message

We present the first reported video of milk fistula. Milk fistula is a rare complication secondary to abscess or breast intervention in lactating women. It is a clinical diagnosis and the treatment is usually conservative, which included cessation of breastfeeding, with a good prognosis.
Not everything is as it seems: neurosarcoidosis presenting as leptomeningitis
Authors: Galnares‐Olalde Javier Andrés , Berebichez‐Fridman Roberto , Gómez‐Garza Gilberto , Mercado Moisés , Moreno‐Sánchez Francisco , Alegría‐Loyola Marco Antonio
Published: February 2018

Key Clinical Message

Involvement of the central nervous system in sarcoidosis is rare; neurosarcoidosis, although unusual, can present as leptomeningitis. The diagnosis is usually difficult because of the vague and broad symptomatology; therefore, a prompt diagnosis should be made, and adequate treatment should be administered to reduce morbidity and mortality.
Hyperammonemic encephalopathy in a patient receiving fluorouracil/oxaliplatin chemotherapy
Authors: Ihoriya Hiromi , Yamamoto Hirotsugu , Yamada Taihei , Tsukahara Kohei , Inoue Kanae , Yumoto Tetsuya , Naito Hiromichi , Nakao Atsunori
Published: February 2018

Key Clinical Message

Hyperammonemia is a rare adverse effect of 5‐fluorouracil (5‐FU) therapy, but can be very serious, even fatal. Physicians must be aware that hyperammonemic encephalopathy sometimes develops as an adverse event after 5‐FU therapy.
A case of immunoglobulin G4‐related aortic diseases
Authors: Sugaya Akira , Misawa Yoshio , Ohki Shin‐ichi , Takazawa Ippei , Uesugi Satoshi
Published: February 2018

Key Clinical Message

A 65‐year‐old man had histories of retroperitoneal fibrosis, membranous nephropathy, and acute coronary syndrome. Chest computed tomography showed an enlarged ascending aorta and type B aortic dissection, and he underwent ascending aorta and arch replacement. A pathological examination of the resected aorta showed immunoglobulin G4‐positive plasma cell infiltration.
A case of late orthostatic headache secondary to lumbar hidden dural fistula 20 months after epidural anesthesia
Authors: Ros Forteza F. J. , Dias da Costa M. A. , Pais R. P.
Published: February 2018

Key Clinical Message

The clinical recognition of CSF fistula is a clinical challenge. We report the case of a young woman, who presented with a late orthostatic headache 20 months after epidural anesthesia. She developed a lumbar dural fistula of CSF confirmed in myelography CT scanning and treated successfully with epidural blood patch.
Effect of Protective Agents upon the Catalytic Property of Platinum Nanocrystals
Authors: Yan Muyu , Wu Tong , Chen Lifang , Yu Yulv , Liu Bo , Wang Yuan , Chen Wenxing , Liu Yan , Lian Chao , Li Yadong
Published: February 2018

“Unprotected” Pt nanocrystals were modified with triphenylphosphine (PPh3), octadecylamine (ODA), poly(vinylpyrrolidone) (PVP), poly(vinyl alcohol) (PVA), and dodecanethiol (DT) to investigate the effect of protective agents on the intrinsic catalytic property of Pt nanocrystals. By evaluating the catalytic performance of these model catalysts for the hydrogenation of para‐chloronitrobenzene (p‐CNB), it was found that direct or indirect interaction between nanocrystals and protective agents imposed a great impact on the catalytic performance of the nanocrystals. Protective agents with different electron‐donating ability (PPh3, ODA, PVP, and PVA) directly altered surface electronic state of Pt nanocrystals to bring the surface Pt atoms into an electron‐rich state, which would exert influence on the hydrogenation course by changing the adsorption and the reactivity of reactant, intermediates, and products. In contrast, DT exerted an indirect influence on the Pt nanocrystals. The coordinated Pt atoms were oxidized by DT to generate cationic Pt species on the surface of nanocrystals, and the cationic species would simultaneously improve the hydrogenation rate and selectivity to para‐chloroaniline by polarizing the N=O bond in the −NO2 group of p‐CNB and altering the electronic state of Pt nanocrystals, respectively. This work provided further insights into nanocatalysis, which is helpful for further design and application of highly efficient nanocrystal catalysts.
Characteristics and Thermal Kinetics of Hydroxyapatite Crystals Doped with Tricarballylic Acid
Authors: Polat Sevgi , Sayan Perviz
Published: February 2018

Hydroxyapatite (HAP) has attracted interest in many fields, e.g., catalysis, water treatment processes, and pharmaceutical industries. HAP crystallization was performed within a batch‐type crystallizer both with and without tricarballylic acid used as additive. The crystals produced in pure media and in the presence of tricarballylic acid were characterized and their thermal degradation was then accomplished in a thermal analyzer in an inert atmosphere. Experimental data was used to calculate the activation energies based on the Kissinger, Flynn‐Wall‐Ozawa, Kissinger‐Akahira‐Sunose, and Starink kinetic models. The results revealed that tricarballylic acid was adsorbed onto the crystal surface, with significant effects on crystal morphology, thermal degradation behavior, and average activation energy.
Electrochemical Evidence for Two Sub‐families of FeNxCy Moieties with Concentration‐Dependent Cyanide Poisoning
Authors: Chung Min Wook , Chon Gajeon , Kim Hyungjun , Jaouen Frédéric , Choi Chang Hyuck
Published: February 2018

Iron‐nitrogen‐carbon (Fe−N−C) catalysts are one of the most promising family of materials for the successful replacement of noble Pt in low‐temperature fuel cells. Despite recent advances in the synthesis, activity, and site‐structure of Fe−N−C catalysts, further improved understanding of the nature of the Fe‐based active sites is still needed. In the present study, the existence of two sub‐families of FeNxCy moieties is revealed by the concentration dependence of cyanide poisoning on a Fe−N−C catalyst only comprising of atomically dispersed iron. The analysis of the activity decrease upon contact with various cyanide concentrations and activity recovery following rinsing with water reveals the presence of two sub‐groups of ORR‐active FeNxCy species. They are discriminated by the reversibility or irreversibility of the cyanide poisoning. From a Mössbauer spectroscopy study and poisoning test on a model compound, Fe(II) phthalocyanine (FePc), we hypothesize that the reversibility/irreversibility of cyanide poisoning is governed by the competitive adsorption of oxygen molecule and cyanide anion. It is proposed that FeNxCy moieties with Fe in low spin state reversibly adsorb cyanide, whereas those with a medium spin state irreversibly adsorb cyanide.
Optimization of Synthetically Versatile Pyridylidene Amide Ligands for Efficient Iridium‐Catalyzed Water Oxidation
Authors: Navarro Miquel , Smith Christene A. , Li Mo , Bernhard Stefan , Albrecht Martin
Published: February 2018

The synthetic versatility of pyridylidene amide (PYA) ligands has been exploited to prepare and evaluate a diverging series of iridium complexes containing C,N‐bidentate chelating aryl‐PYA ligands for water oxidation catalysis. The phenyl‐PYA lead structure 1 was modified (i) electronically through introduction of one, two, or three electron‐donating methoxy substituents on the aryl ring, (ii) by incorporating long aliphatic chains to the pyridyl fragment of the PYA unit, and (iii) by altering the PYA positions from para‐PYA to its ortho‐ and meta‐isomers. Electrochemistry indicated no substantial electronic effect of the aliphatic chains, and only minor changes of the electron density at iridium when modifying the aryl ligand site, yet substantial alteration if the PYA ligand is the ortho‐ (E1/2=+0.72 V), para‐ (E1/2=+0.64 V), or meta‐isomer (E1/2=+0.56 V vs. saturated calomel electrode; SCE). In water oxidation catalysis, the long alkyl chains did not induce any rate enhancement compared with the phenyl‐PYA lead compound, whereas MeO groups incorporated in the aryl group enhanced the catalytic activity from a turnover frequency (TOFmax)=1600 h−1 in the original Ph‐PYA system gradually as more MeO groups were introduced up to a TOFmax=3300 h−1 for a tris(MeO)‐substituted aryl‐PYA system. The variation of the PYA substitution had only a minor impact on catalytic activity and revealed only a weak trend in the sequence ortho>meta>para. The high activity of the tris(MeO) system and the ortho‐PYA isomer were attributed to efficient hydrogen bonding, which assists O−H bond activation and proton transfer. Remarkably, merging of the two optimized motifs, that is, an aryl unit with three MeO substituents and the PYA as the ortho isomer, into a single new aryl‐PYA ligand system failed to improve the catalytic activity. Computational analysis suggests too much congestion at the active site, which hinders catalytic turnover. These results illustrate the complexity of ligand design and the subtle effects at play in water oxidation catalysis.
12‐Vertex Zwitterionic Bis‐phosphonium‐nido‐carborates through Ring‐Opening Reactions of 1,2‐Diphosphetanes
Authors: Schulz Jan , Kreienbrink Anika , Coburger Peter , Schwarze Benedikt , Grell Toni , Lönnecke Peter , Hey‐Hawkins Evamarie
Published: February 2018

Carborane‐substituted 1,2‐diphosphetanes (Ia,b) react with elemental lithium in THF with cleavage of the P−P bond to give a deep red solution from which, in the case of Ia, red crystals of a lithiated intermediate, [{1‐Li(THF)PtBu‐6‐PtBu‐4,1,6‐closo‐Li(THF)C2B10H10}{Li(THF)3}]2⋅2 THF (2 a), are obtained. The compound is dimeric, C2‐symmetric and contains six lithium and four phosphorus atoms. Two lithium atoms cap the six‐membered C2B4 faces, resulting in two 13‐vertex closo‐clusters (according to Wade's rules) with docosahedral geometry. The addition of methyl iodide resulted in the formation of zwitterionic bis‐phosphonium‐nido‐carborates 7,10‐bis(tert‐butyldimethylphosphonium)dodecahydro‐7,10‐dicarba‐nido‐dodecaborate(2−) (1 a) and 7,10‐bis(N,N‐diisopropylaminodimethylphosphonium)dodecahydro‐7,10‐dicarba‐nido‐dodecaborate(2−) (1 b) in moderate to good yields. Compounds 1 a and 1 b exhibit short Ccluster−P bonds and large Ccluster⋅⋅⋅Ccluster distances in the solid state. Further insight into the ring opening and reduction potential of the alkyl halide was obtained from methylation reactions of different 1,2‐bis‐phosphinocarboranes. The reaction of rac‐/meso‐1,2‐bis(tert‐butylmethylphosphino)‐1,2‐dicarba‐closo‐dodecaborane(12) (3 a) with two equivalents of methyl iodide also resulted in the formation of 1 a (as shown by NMR spectroscopy), whereas the reaction of 1,2‐bis(diphenylphosphino)‐1,2‐dicarba‐closo‐dodecaborane(12) with methyl triflate afforded the phosphonium salt 1‐methyl‐diphenylphosphonium‐2‐diphenylphosphino‐1,2‐dicarba‐closo‐dodecaborane(12) triflate (4) without reduction of the cluster.
Self‐Assembly of a Guanosine Derivative To Form Nanostructures and Transmembrane Channels
Authors: Das Rabindra Nath , Kumar Y. Pavan , Kumar S. Arun , Schütte Ole Mathis , Steinem Claudia , Dash Jyotirmayee
Published: February 2018

We herein report the self‐assembly of a lipophilic bromoguanosine derivative (G1) in homogeneous solution, in the solid state and in planar bilayer membranes. The self‐assembly of G1, driven by H‐bonding and π–π stacking interactions can form different nano‐structures depending on incubation time. The G1 nanostructure is able to bind a bioactive dye like Rose Bengal. In crystal state, it shows ribbon type H‐bonding pattern and exhibits birefringence in polarized light. And further, the self‐assembled nanostructure of G1 can form discrete transmembrane ion channels in lipid bilayer membranes, enabling passage of potassium ions.
Cation‐Triggered Stannate(II)/Stannylenoid/Stannylene Conversion
Authors: Zhao Hui , Li Junxia , Xiao Xu‐Qiong , Kira Mitsuo , Li Zhifang , Müller Thomas
Published: February 2018

The reaction of dipotassio‐tetrasilan‐1,4‐diide (4) with anhydrous SnCl2 at low temperature results in the formation of a five‐membered cyclic potassio chlorostannate(II) ([(18‐C‐6)K](1)). By careful cation exchange reactions, it was transformed into the sodium chlorostannylenoid 2 (by using Na2[B12Cl12]) or into the non‐stabilized cyclic bissilylstannylene 3 (through applying Li[Al(OC(CF3)3)4]). The increasing Lewis basicity of the bissilylstannylene 3 was analyzed by combined methods of DFT calculations and NMR spectroscopy and substantiated by the synthesis of the corresponding iron carbonyl complexes 7 and 8 from the chlorostannate 1 and the stannylene 3, respectively.
Comprehensive investigation into the interconversion of C‐2 diastereomers of naringin
Authors: Yao Hongliang , Su Weiwei , Lin Linhuo , Pan Wenjun , Zeng Xuan , Li Panlin
Published: February 2018

Naringin is a flavanone that widely presents on daily diet and traditional medicinal materials. The ratios of naringin C‐2 diastereomers are found different in reported samples, thus suspiciously leading to various functions. In this study, we measured the interconversion of C‐2 diastereomers intensively with ultimate high‐performance liquid chromatography and circular dichroism spectra. We examined the diastereomeric naringins in fresh citrus fruit, Huajuhong decoction pieces, and naringin tablet; evaluated the impact of tablet production procedures in factory; and monitored the rapid racemization in incubation. The results not only confirmed that enzyme, temperature, and pH condition could influence the interconversion but also demonstrated that diverse ratios of diastereomers showed limited influence on metabolic behaviors of naringin in the blood, which consequently cause comparable bioactivities. This study could provide comprehensive understanding of diastereomeric interconversion and provide useful reference for drug development.
Understanding the flow behaviour of copolymer and associative polymers in porous media using extensional viscosity characterization: Effect of hydrophobic association
Authors: Azad Madhar Sahib , Dalsania Yogesh , Trivedi Japan J.
Published: February 2018

Associative polymer (AP) and hydrolyzed polyacrylamide (HPAM), the two commonly used polymers for heavy oil recovery, are reported to exhibit very different flow behaviour in porous media despite having similar shear viscosity. The kind of hydrophobic association (intramolecular or intermolecular) that AP exhibit is concentration dependent and will influence both shear and elongational flow in the porous media. To understand flow behaviour of these two polymers in porous media, the role of hydrophobic association on shear and extensional rheology and its effect on the resistance factor (RF) and residual resistance factor in porous media are investigated over a non‐associating HPAM polymer. The results suggest that shear rheology and the Deborah number cannot explain the porous media flow behaviour. However, direct measurements of extensional properties using a capillary breakup extensional rheometer have shown the marginal difference between two polymers at a lower concentration (1000 ppm) and the considerable difference at a higher concentration (2000 ppm), indicating an intramolecular and intermolecular association, respectively. These results are in accordance with porous media observations where both polymers have shown a similar RF at 1000 ppm. Whereas, at 2000 ppm AP showed a much higher RF at low/intermediate fluxes, and a similar RF at high flux, suggesting the transformation from intermolecular association to intramolecular association. The significant drop in the extensional viscosity at high strain rates after exhibiting the maxima explains this behaviour.
ZIF‐based water‐stable mixed‐matrix membranes for effective CO2 separation from humid flue gas
Authors: Sarfraz Muhammad , Ba‐Shammakh M.
Published: February 2018

Water stable mixed‐matrix membranes (MMMs) were developed to help control global warming by capturing and sequestrating carbon dioxide (CO2) from humid flue gas originated from burning of fossil fuels. MMMs of different compositions were prepared by doping glassy polymer Ultrason® S 6010 (US) with nanocrystals of zeolitic imidazolate frameworks (ZIF‐302) in varying degrees. A solution‐casting technique was used to fabricate various MMMs to optimize their CO2 capturing performance from both dry and wet gases. The prepared composite membranes indicated enhanced filler‐polymer interfacial adhesion, consistent distribution of nanofiller, and thermally stable matrix configuration. CO2 permeability of the membranes was enhanced as demonstrated by gas sorption and single gas permeation tests carried out under dry and moist circumstances. As compared to neat Ultrason® membrane, CO2 permeability and expected CO2/N2 permselectivity of the mixed membrane doped with 40 g/g ZIF‐302 nanocrystals were significantly enhanced. In contrast to the majority of previously reported membranes, key features of fabricated MMMs include their structural stability under humid conditions coupled with better and unaffected gas separation performance.
Application of Mono‐ and Disaccharides in Drug Targeting and Efficacy
Authors: Yuan Si S. , Li Mao L. , Chen Jian S. , Zhou Li , Zhou Wen
Published: February 2018

Carbohydrates and their conjugates play important roles in many biological processes including fertilization, differentiation, development, immune response, and infection. Their activities are largely dependent on the properties of terminal mono‐ or disaccharides. Galactose, mannose, fucose, glucose, sialic acid, etc., are commonly used as powerful scaffolds installed on drug molecules for targeting specific tissues including brain, liver, and cancers, and as epitopes for enhancing the targeting of various vaccines. This review focuses on the influence of their structural variations, including changes in sugar type, substituent groups and their positions, as well as length of linker portion, on the targeting of drugs or their efficacy. Particular attention is paid to the targeting properties of mono‐ and disaccharides applied in drug design and discovery.
A survey on security issues in services communication of Microservices‐enabled fog applications
Authors: Yu Dongjin , Jin Yike , Zhang Yuqun , Zheng Xi
Published: February 2018

Fog computing is used as a popular extension of cloud computing for a variety of emerging applications. To incorporate various design choices and customized policies in fog computing paradigm, Microservices is proposed as a new software architecture, which is easy to modify and quick to deploy fog applications because of its significant features, ie, fine granularity and loose coupling. Unfortunately, the Microservices architecture is vulnerable due to its wildly distributed interfaces that are easily attacked. However, the industry has not been fully aware of its security issues. In this paper, a survey of different security risks that pose a threat to the Microservices‐based fog applications is presented. Because a fog application based on Microservices architecture consists of numerous services and communication among services is frequent, we focus on the security issues that arise in services communication of Microservices in four aspects: containers, data, permission, and network. Containers are often used as the deployment and operational environment for Microservices. Data is communicated among services and is vital for every enterprise. Permission is the guarantee of services security. Network security is the foundation for secure communication. Finally, we propose an ideal solution for security issues in services communication of Microservices‐based fog applications.
Optimizing Structural, Microhardness, Surface Growth Mechanism, Luminescence and Thermal Traits of KH2PO4 Crystal Exploiting Multidirectional H‐Bonding Quality of Dopant Tartaric Acid
Authors: Anis Mohd , Baig Mirza Irshad , Pandian Muthu Senthil , Ramasamy P. , AlFaify Salem , Ganesh Venga , Muley Gajanan G. , Ghramh Hamed Ali
Published: February 2018

High‐end nonlinear optical devices demand superior quality KH2PO4 crystal and to meet this necessity slow solvent evaporation technique is employed to grow optical quality potassium dihydrogen orthophosphate (KH2PO4, KDOP) crystal by doping tartaric acid (TA) and special attention is devoted to optimize the defect influenced properties of KDOP crystal. The incorporation of TA in KDOP crystal matrix is evaluated by employing energy dispersive spectroscopic technique. The crystalline phase and structural dimensions of pure and TA doped KDOP crystal is evaluated by means of powder X‐ray diffraction analysis. The luminescence behavior of TA doped KDOP crystal is examined in visible region and violet colored emission is evidenced at 408 nm. The Vickers microhardness studies are carried out to uncover the constructive influence of TA on hardness and elastic stiffness coefficient of KDOP crystal. Impressive role of TA in minimizing defect density and improving the surface growth mechanism of KDOP crystal is explored by chemical etching analysis. The thermogravimetric analysis curve is traced within 30–650 °C and TA doped KDOP crystal is found thermally stale up to 233 °C. The results are appraised to propose the suitability of TA doped KDOP crystal for distinct applications.