bluuebunny/crossref_metadata_2025 huggingface dataset:
Silica Gel and its Derivatization for Liquid Chromatography
Authors: Skoczylas Magdalena , Krzemińska Katarzyna , Bocian Szymon , Buszewski Bogusław
Published: January 2017

In this article, we review the preparation methods of silica and silica hybrid materials, as well as their surface modification and application in liquid chromatography (LC). First we discuss the synthesis and properties of silica and silica hybrids. In the second part, we present the modification methods leading to their stationary phases. The current state of the art of the stationary phase's synthesis during silanization, hydrosilation, and coating is discussed. A detailed characterization of both native silica and its modifications is provided. The most common stationary phases for reversed‐phase, normal‐phase, and hydrophilic interaction LC are featured. Unconventional stationary phases, for example, with bonded cholesterol molecules, are also included. The potential applications of the described stationary phases are presented.
Coordination Chemistry and Applications of Phenolic Thiacalixarene–Metal Complexes
Authors: Cragg Peter J. , Marcos Paula M.
Published: January 2017

Thiacalixarenes are members of the calixarene family in which sulfur has replaced one or more of the methylene bridges between the phenolic moieties of the macrocycles. Oxidation of the thiacalixarenes leads to sulfinyl and sulfonyl homologs. The incorporation of sulfur affects the metal‐binding affinities of these calixarenes over their all‐carbon analogs through the abilities of the heteroatoms both to bind directly and to influence lower rim phenolic binding. Other binding motifs are possible for the oxidized thiacalixarenes leading to a vast array of complexes with metal cations. This chapter covers the literature concerning thiacalixarenes containing free OH groups at the lower rim since they were first reported. Their coordination chemistry toward alkali, alkaline earth, transition, heavy, lanthanide, and actinide metals is discussed. Examples of crystal structures of these metal complexes are given, as well as brief descriptions of their applications in fields such as catalysis, transition‐metal extraction, and cation transport.
Antinuclear Matrix Protein 2 Autoantibodies and Edema, Muscle Disease, and Malignancy Risk in Dermatomyositis Patients
Authors: Albayda Jemima , Pinal‐Fernandez Iago , Huang Wilson , Parks Cassie , Paik Julie , Casciola‐Rosen Livia , Danoff Sonye K. , Johnson Cheilonda , Christopher‐Stine Lisa , Mammen Andrew L.
Published: January 2017

Objective

Dermatomyositis (DM) patients typically present with proximal weakness and autoantibodies that are associated with distinct clinical phenotypes. We observed that DM patients with autoantibodies recognizing the nuclear matrix protein NXP‐2 often presented with especially severe weakness. The aim of this study was to characterize the clinical features associated with anti–NXP‐2 autoantibodies.

Methods

There were 235 DM patients who underwent testing for anti–NXP‐2 autoantibodies. Patient characteristics, including muscle strength, were compared between those with and without these autoantibodies. The number of cancer cases observed in anti–NXP‐2‐positive subjects was compared with the number expected in the general population.

Results

Of the DM patients, 56 (23.8%) were anti–NXP‐2‐positive. There was no significant difference in the prevalence of proximal extremity weakness in patients with and without anti–NXP‐2. In contrast, anti–NXP‐2‐positive patients had more prevalent weakness in the distal arms (35% versus 20%; P = 0.02), distal legs (25% versus 8%; P < 0.001), and neck (48% versus 23%; P < 0.001). Anti–NXP‐2‐positive subjects were also more likely to have dysphagia (62% versus 35%; P < 0.001), myalgia (46% versus 25%; P = 0.002), calcinosis (30% versus 17%; P = 0.02), and subcutaneous edema (36% versus 19%; P = 0.01) than anti–NXP‐2‐negative patients. Five anti–NXP‐2‐positive subjects (9%) had cancer‐associated myositis, representing a 3.68‐fold increased risk (95% confidence interval 1.2–8.6) compared to the expected prevalence in the general population.

Conclusion

In DM, anti–NXP‐2 autoantibodies are associated with subcutaneous edema, calcinosis, and a muscle phenotype characterized by myalgia, proximal and distal weakness, and dysphagia. As anti–NXP‐2‐positive patients have an increased risk of cancer, we suggest that they undergo comprehensive cancer screening.
Sensitivity and Specificity of Radiographic Scoring Instruments for Detecting Change in Axial Psoriatic Arthritis
Authors: Ibrahim Ali , Gladman Dafna D. , Thavaneswaran Arane , Eder Lihi , Helliwell Philip , Cook Richard J. , Chandran Vinod
Published: January 2017

Objective

There is no widely recognized method used to assess axial disease in psoriatic arthritis (PsA). We aimed to determine the sensitivity to change of the Bath Ankylosing Spondylitis Radiology Index for the spine (BASRI‐s), the modified Stoke Ankylosing Spondylitis Spine Score (mSASSS), the Radiographic Ankylosing Spondylitis Spine Score (RASSS), and the PsA Spondylitis Radiology Index (PASRI) in axial PsA.

Methods

Radiographs of 105 patients with axial PsA were retrieved for 2 time points at least 2 years apart and subsequently anonymized. All radiographs were scored by 3 rheumatologists blinded to name and order of examination using an electronic application that allowed recording of disease manifestations specific to axial PsA and automatically calculated the BASRI‐s, mSASSS, RASSS, and PASRI scores. An independent expert determined whether there was true radiographic progression from an overall impression after viewing the radiographs with knowledge of chronologic order. The sensitivity, specificity, and odds ratios for every 1‐unit increase in the scores were determined to identify true change.

Results

Of the patients studied, 25 (24%) showed progression, as determined by the independent expert. The respective sensitivity and specificity values for an increase in score to detect true change were as follows: 0.48 and 0.78 (BASRI‐s), 0.52 and 0.84 (mSASSS), 0.44 and 0.84 (RASSS), and 0.52 and 0.74 (PASRI). Logistic regression analyses showed that an increase of 1 point in the respective scores was associated with the following odds ratios for identifying true progression: BASRI‐s 3.0, mSASSS 5.27, RASSS 3.70, and PASRI 3.06.

Conclusion

Available scoring systems for quantifying radiographic axial PsA have moderate sensitivity but high specificity for detecting true change.
The Hackable City: Citymaking in a Platform Society
Authors: de Waal Martijn , de Lange Michiel , Bouw Matthijs
Published: January 2017

Can computer hacking have positive parallels in the shaping of the built environment? The Hackable City research project was set up with this question in mind, to investigate the potential of digital platforms to open up the citymaking process. Its cofounders Martijn de Waal, Michiel de Lange and Matthijs Bouw here outline the tendencies that their studies of collaborative urban development initiatives around the world have revealed, and ask whether knowledge sharing and incremental change might be a better way forward than top‐down masterplans.
VoiceOver: Citizen Empowerment Through Cultural Infrastructure
Authors: Haque Usman
Published: January 2017

In the relentless drive for efficiency, our lives are increasingly dominated by decision‐making algorithms imposed from above. As Usman Haque observes, this leaves us feeling disenfranchised. Umbrellium, the team he cofounded to design and deploy participatory platforms, is working to re‐establish community engagement. Its ongoing VoiceOver project in the village of Horden, County Durham, shows how people can be encouraged to connect beyond their usual sphere and to make collective decisions, enhancing their sense of ownership of the outcomes.
The Image of a Data City: Studying the Hyperlocal with Social Media
Authors: Manovich Lev , Indaco Agustin
Published: January 2017

Sharing photos, videos and comments on social media may seem an idle pastime, but it is not without its uses where urban design is concerned. Analysing such posts can yield helpful indicators as to how people experience the built environment. Lev Manovich and Agustin Indaco, of the Software Studies Lab at the University of California, San Diego and the Graduate Center, City University of New York, here outline two of the Lab's recent research projects, which have involved examining extensive Instagram data from various cities around the globe.
Tell 'Em They're Dreamin’
Authors: Burry Mark
Published: January 2017

Could 4D hyperlocal activism be the ultimate tool for popular resistance? This Counterpoint's title quotes the response of the main protagonist in Rob Sitch's 1997 film The Castle to developers' attempts at the compulsory purchase of his home. His act of refusal follows on from the decades‐earlier writings of Herbert Marcuse and Ralph Adams Cram on the perils of capitalism and how they might be overcome. With reference to these, Mark Burry, a practising architect and Professor of Urban Futures at the University of Melbourne, considers the impact of technological enfranchisement on liveability.
Rock Salt Ni/Co Oxides with Unusual Nanoscale‐Stabilized Composition as Water Splitting Electrocatalysts
Authors: Fominykh Ksenia , Tok Gülen Ceren , Zeller Patrick , Hajiyani Hamidreza , Miller Thomas , Döblinger Markus , Pentcheva Rossitza , Bein Thomas , Fattakhova‐Rohlfing Dina
Published: January 2017

The influence of nanoscale on the formation of metastable phases is an important aspect of nanostructuring that can lead to the discovery of unusual material compositions. Here, the synthesis, structural characterization, and electrochemical performance of Ni/Co mixed oxide nanocrystals in the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is reported and the influence of nanoscaling on their composition and solubility range is investigated. Using a solvothermal synthesis in tert‐butanol ultrasmall crystalline and highly dispersible Ni
x
Co1−

x
O nanoparticles with rock salt type structure are obtained. The mixed oxides feature non‐equilibrium phases with unusual miscibility in the whole composition range, which is attributed to a stabilizing effect of the nanoscale combined with kinetic control of particle formation. Substitutional incorporation of Co and Ni atoms into the rock salt lattice has a remarkable effect on the formal potentials of NiO oxidation that shift continuously to lower values with increasing Co content. This can be related to a monotonic reduction of the work function of (001) and (111)‐oriented surfaces with an increase in Co content, as obtained from density functional theory (DFT+U) calculations. Furthermore, the electrocatalytic performance of the Ni
x
Co1−

x
O nanoparticles in water splitting changes significantly. OER activity continuously increases with increasing Ni contents, while HER activity shows an opposite trend, increasing for higher Co contents. The high electrocatalytic activity and tunable performance of the nonequilibrium Ni
x
Co1−

x
O nanoparticles in HER and OER demonstrate great potential in the design of electrocatalysts for overall water splitting.
Short Synthetic α‐Helical‐Forming Peptide Amphiphiles for Fungal Keratitis Treatment In Vivo
Authors: Wu Hong , Liu Shaoqiong , Wiradharma Nikken , Ong Zhan Yuin , Li Yan , Yang Yi Yan , Ying Jackie Y.
Published: January 2017

The emergence of fungal keratitis is on the rise globally. However, current antifungal therapeutics are ineffective in severe keratomycosis. Previously reported α‐helical peptides comprising 8–14 amino acids demonstrate broad‐spectrum antimicrobial activity both in vitro and in vivo. Here, α‐helical peptides of the optimized sequences are investigated for antifungal biofilm in vitro and in vivo using a fungal biofilm‐caused mouse keratitis model. The peptides with the optimal composition demonstrate higher α‐helical propensity and improve antifungal activity in dispersing Candida albicans biofilm in vitro. Moreover, the optimized α‐helical peptides are not only effective in treating C. albicans biofilm‐induced keratitis in mice, they are also nontoxic to the mice eyes. These peptides have the potential to be developed as antifungal agents for the treatment of C. albicans biofilm‐caused keratitis.
Xenogeneic Bio‐Root Prompts the Constructive Process Characterized by Macrophage Phenotype Polarization in Rodents and Nonhuman Primates
Authors: Li Hui , Sun Jingjing , Li Jie , Yang Hefeng , Luo Xiangyou , Chen Jinlong , Xie Li , Huo Fangjun , Zhu Tian , Guo Weihua , Tian Weidong
Published: January 2017

Tissue or organ regeneration using xenogeneic matrices is a promising approach to address the shortage of donor matrices for allotransplantation. Success of such approach has been demonstrated to correlate with macrophage‐mediated fibrotic homeostasis and tissue remodeling. The previous studies have demonstrated that treated dentin matrix (TDM) could be a suitable bioactive substrate for allogeneic tooth root regeneration. This study constructed xenogeneic bioengineered tooth root (bio‐root) via a combination of porcine TDM (pTDM) with allogeneic dental follicle cells (DFCs). Macrophage phenotypes are used to evaluate the remodeling process of xenogeneic bio‐roots in vitro and in vivo. pTDM can facilitate odontoblast differentiation of human derived DFCs. Xenogeneic bio‐roots in rat subcutaneous tissue prompt constructive response via M1 macrophage infiltration during early postimplantation stages and increase restorative M2 phenotype at later stages. After implantation of bio‐roots into jaws of rhesus monkeys for six months, periodontal ligament‐like fibers accompanied by macrophage polarization are observed, which are positive for COL‐1, Periostin, βIII‐tubulin and display such structures as fibroblasts and blood vessels. The reconstructed bio‐root possesses biomechanical properties for the dissipation of masticatory forces. These results support that xenogeneic bio‐root could maintain fibrotic homeostasis during remodeling process and highlight the potential application of xenogeneic matrices in regenerative medicine.
Substrate‐Controlled Diastereoselective Synthesis of Sugar‐Based Chlorinated Perhydrofuro[2,3‐b]pyrans via Copper(I)‐Catalyzed Radical Cyclization
Authors: Ram Ram N. , Kumar Neeraj , Gupta Dharmendra Kumar
Published: January 2017

The work describes the first copper(I) chloride/2,2′‐bipyridine‐catalyzed atom transfer radical cyclization (ATRC) of unsaturated carbohydrate‐derived chloroacetals to generate chlorinated perhydrofuro[2,3‐b]pyrans via an effective diastereoselective route. Various glycals (glucal, galactal and lactal) underwent the Ferrier rearrangement with 2,2,2‐trichloroethanols to give acetal precursors stereoselectively, R‐selective with galactal in contrast to S‐selective with glucal. The radical cyclization of the Ferrier products occurred smoothly to afford cis‐fused bicyclic products with the transfer of the chlorine atom at the non‐anomeric carbon in the cyclized radical intermediate predominantly from the equatorial direction. The carbohydrate templates controlled the stereochemistry of both Ferrier rearrangement and ATRC steps. The stereostructures of the products were also supported by single crystal X‐ray diffraction crystallography. The products possess biologically important structural segments such as a glycosidic linkage, a fused bicyclic acetal unit and a chlorosugar unit which are potential sources for biological studies and further synthetic elaborations.

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Non‐Covalent Carbonyl‐Directed Heck–Matsuda Desymmetrizations: Synthesis of Cyclopentene‐Fused Spirooxindoles, Spirolactones, and Spirolactams
Authors: Kattela Shivashankar , Heerdt Gabriel , Correia Carlos R. D.
Published: January 2017

Enantioselective carbonyl‐directable Heck reactions using aryldiazonium salts were developed with the aim to construct chiral quaternary spiro centers in an efficient manner. Five‐ and six‐membered spirooxindoles, spirolactones, and spirolactams (36 examples) were obtained in good to excellent isolated yields with diastereoselectivities ranging from 13:1 to >20:1, and enantiomeric excesses up to 99% in short reaction times (1.0–1.5 h) under mild conditions (40 °C). A rationale for the diastereo‐ and enantioselectivity based on an unprecedented non‐covalent carbonyl group directing effect is also presented, and supported by computational calculations.

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Preparation of Electrophilic Trifluromethylthio Reagents from Nucleophilic Tetramethylammonium Trifluoromethylthiolate
Authors: Kovács Szabolcs , Bayarmagnai Bilguun , Goossen Lukas J.
Published: January 2017

A straightforward synthetic entry to the principal classes of electrophilic trifluoromethylthiolating agents is presented. It draws on inexpensive, shelf‐stable tetramethylammonium trifluoromethylthiolate (Me4N–SCF3) as the SCF3 source in the place of stoichiometric coinage metal‐SCF3 complexes.

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Development of a chemiluminescence sensor based on molecular imprinting technology for the determination of trace monocrotophos in vegetables
Authors: Wang Shoumin , Zhao Peng , Li Ningyang , Qiao Xuguang , Xu Zhixiang
Published: January 2017

In this study, a new sensor of molecularly imprinted solid‐phase extraction coupled with flow‐injection chemiluminescence for the detection of monocrotophos was fabricated. The molecularly imprinted polymer was synthesized by the bulk polymerization, using monocrotophos, methacrylic acid, and ethylene glycol dimethacrylate as the template molecule, functional monomer, and cross‐linker, respectively. The adsorption and recognition ability of the imprinted polymer toward monocrotophos was investigated. Factors influencing preconcentration of the analytes and sensitivity of the method were optimized. Under the optimal conditions, the chemiluminescence intensity was linearly proportional to the concentration of monocrotophos range from 0.0023 to 10 mg/L, and the limit of detection of the method was 0.001 mg/L. Rape (Brassica napus) and pakchoi (Brassica rapa subsp. chinensis) samples spiked with monocrotophos at three levels were analyzed by the developed method with recoveries between 89.3% and 105.9%. This method was successfully applied to the determination of monocrotophos in spinach samples, and the results were verified by gas chromatography method.
Rigorous analysis of optical forces between two dielectric planar waveguides immersed in dielectric fluid media
Authors: Rodrigues Janderson R. , Almeida Vilson R.
Published: January 2017

This work presents a rigorous analysis of optical forces between planar waveguides immersed in an arbitrary background medium. This approach exploits the Minkowski stress tensor formulation, which is compared with a normalized version of the dispersion relation method, showing excellent results agreement for different dielectric fluid media. Due to slot‐waveguide effect, optical forces from TM modes are more sensitive to changes in the fluid refractive index than the TE counterparts. Furthermore, the repulsive optical force from the antisymmetric TM1 mode becomes stronger for higher refractive indexes, whereas the attractive force of the symmetric TM0 mode becomes weaker. The methodology and results presented in this work provide a rigorous analysis of nano‐optomechanical devices actuated by optical forces in a broad range of materials and applications. Therefore, this study may impact areas of light‐induced interactions presenting novel optofluidic and optomechanical functionalities, thus finding applications in nanoscale transport, sensing and manipulation.

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An Isolable Silicon Dicarbonate Complex from Carbon Dioxide Activation with a Silylone
Authors: Burchert Alexander , Yao Shenglai , Müller Robert , Schattenberg Caspar , Xiong Yun , Kaupp Martin , Driess Matthias
Published: January 2017

The first isolable molecular silicon dicarbonate complex (bis‐NHC)Si(CO3)2 2 (bis‐NHC=H2C[{NC(H)=C(H)N(Dipp)}C:]2, Dipp=2,6‐iPr2C6H3) was synthesized by facile reaction of the bis‐N‐heterocyclic carbene stabilized silylone (bis‐NHC)Si 1, bearing a zero‐valent silicon atom, with carbon dioxide. The monomeric silicon dioxide complex (bis‐NHC)SiO2 3 supported by the bis‐NHC ligand was proposed as a key intermediate resulting from double oxygenation of the zero‐valent silicon atom in 1 by two molar equivalents of CO2 under liberation of CO; its subsequent Lewis acid–base reaction with CO2 leads to 2 which has been fully characterized including an single‐crystal X‐ray diffraction analysis. Its electronic structure, spectroscopic data and the thermochemistry of the formation have been studied quantum‐chemically.
Reversible Photoactivated Phosphorescence of Gold(I) Arylethynyl Complexes in Aerated DMSO Solutions and Gels
Authors: Wan Shigang , Lu Wei
Published: January 2017

Phosphorescence in fluid solutions at ambient temperature is usually quenched by molecular oxygen via energy transfer, and singlet oxygen is concomitantly sensitized. The long‐lived phosphorescence of a series of AuI arylethynyl complexes with tunable emission energies in aerated dimethyl sulfoxide (DMSO) solutions can be completely and repeatedly switched on by controlled photoirradiation. A trace amount of DMSO oxidation by the sensitized singlet oxygen is proposed to lead to a depletion of molecular oxygen in the local microenvironment of the AuI phosphor in the photoactivation processes. Harnessing the photoactivated phosphorescence and using UV light as a non‐contact pen, a writing–erasing–rewriting prototype has been demonstrated with a DMSO gel containing AuI arylethynyl complexes.
Entfernung von organischen, anorganischen und mikrobiellen Schadstoffen aus Wasser durch immobilisierte Polyoxometallat‐basierte ionische Flüssigkeiten (POM‐SILPs)
Authors: Herrmann Sven , De Matteis Laura , de la Fuente Jesús M. , Mitchell Scott G. , Streb Carsten
Published: January 2017

Die gleichzeitige Entfernung organischer, anorganischer und mikrobieller Schadstoffe aus Wasser durch ein einziges Material bietet deutliche Vorteile, insbesondere für den dezentralen Einsatz in entlegenen Regionen. Dieser Beitrag beschreibt ein Komposit, welches diese Aufgabe erfüllt. Es besteht aus Polyoxometallat‐basierte ionischen Flüssigkeiten (POM‐ILs) die auf porösem Silika immobilisiert sind (POM‐SILP; supported ionic liquid phase) Dazu wurde eine wasserunlösliche POM‐IL bestehend aus antimikrobiellen Alkylammonium‐Kationen und Polyoxometallat‐Anionen mit einer Metallbindungsstelle auf porösem Silika abgeschieden. Mit dem Komposit lassen sich in einem einfachen Filtrationsprozess Schwermetallkationen, Radionuklide, organische und mikrobielle Verunreinigungen aus Wasser entfernen. Die neue Materialklasse zeigt, wie molekulares Design und Materialentwicklung zu innovativen Kompositen für die Wasseraufbereitung führen.
Conformational SERS Classification of K‐Ras Point Mutations for Cancer Diagnostics
Authors: Morla‐Folch Judit , Gisbert‐Quilis Patricia , Masetti Matteo , Garcia‐Rico Eduardo , Alvarez‐Puebla Ramon A. , Guerrini Luca
Published: January 2017

Point mutations in Ras oncogenes are routinely screened for diagnostics and treatment of tumors (especially in colorectal cancer). Here, we develop an optical approach based on direct SERS coupled with chemometrics for the study of the specific conformations that single‐point mutations impose on a relatively large fragment of the K‐Ras gene (141 nucleobases). Results obtained offer the unambiguous classification of different mutations providing a potentially useful insight for diagnostics and treatment of cancer in a sensitive, fast, direct and inexpensive manner.
Polyethylenimine‐functionalized multiwalled carbon nanotube for the adsorption of hydrogen sulfide
Authors: Chu Yineng , Tang Donglin , Ke Zhijun , Ma Jie , Li Ruihai
Published: January 2017

Functionalized multiwalled carbon nanotubes (MWCNTs) were synthesized with ethane diamine and polyethylenimine (PEI) with molecular weights of 1800 [MWCNT‐PEI weight‐average molecular weight (Mw) = 1800] and 70,000 (MWCNT‐PEI Mw = 70,000), respectively. The structures and properties of the ethane diamine functionalized MWCNTs and PEI‐functionalized MWCNTs were characterized by Raman spectroscopy, thermogravimetric analysis, X‐ray powder diffraction, and scanning electron microscopy. An increase with the D/G (D, Disorder band; G, Graphite) ratio of the functionalized MWCNTs in the Raman spectra proved that the ethane diamine and PEI were successfully bonded to the surface of the pristine MWCNTs. The results of TGA also confirmed this. In addition, the structure of the functionalized MWCNTs showed no significant changes compared with the pristine MWCNTs; this was confirmed by X‐ray powder diffraction. Hydrogen sulfide (H2S) sorption on the functionalized MWCNTs was studied by UV spectroscopy. As expected, the results of UV spectroscopy shows that the MWCNTs bonded with higher molecular weight PEI had a more excellent H2S adsorption efficiency than those bonded with low‐molecular‐weight PEI and ethane diamine, a micromolecular amine. The effects of the pH and temperature on the adsorption of H2S were also studied. Under the conditions investigated, the maximum first‐time H2S adsorption efficiency of 1.94 mmol/g was observed for MWCNT‐PEI (Mw = 70,000) in the 60 mg/L sodium hydrosulfide (NaHS) aqueous solution. In addition, the H2S reversible adsorption of the functionalized MWCNTs was conducted, and the second‐time H2S adsorption efficiency of MWCNT‐PEI (Mw = 70,000) reached 1.83 mmol/g in the 60 mg/L NaHS aqueous solution. The results demonstrate that the MWCNTs decorated with high‐molecular‐weight PEI were potentially excellent and reversible H2S adsorbents. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44742.
The Controllability of Fractional Damped Stochastic Integrodifferential Systems
Authors: Sathiyaraj T. , Balasubramaniam P.
Published: January 2017

In this paper, the complete controllability is investigated for nonlinear fractional damped stochastic integrodifferential system in finite dimensional space. Using linear controllability theory, sufficient conditions ensuring complete controllability are derived based on controllability Grammian matrix which is defined by Mittag‐Leffler matrix function and fixed‐point techniques. Finally, two numerical examples are given to verify the proposed conditions.
Clinical trial design as a decision problem
Authors: Müller Peter , Xu Yanxun , Thall Peter F.
Published: January 2017

The intent of this discussion is to highlight opportunities and limitations of utility‐based and decision theoretic arguments in clinical trial design. The discussion is based on a specific case study, but the arguments and principles remain valid in general. The example concerns the design of a randomized clinical trial to compare a gel sealant versus standard care for resolving air leaks after pulmonary resection. The design follows a principled approach to optimal decision making, including a probability model for the unknown distributions of time to resolution of air leaks under the two treatment arms and an explicit utility function that quantifies clinical preferences for alternative outcomes. As is typical for any real application, the final implementation includes some compromises from the initial principled setup. In particular, we use the formal decision problem only for the final decision, but use reasonable ad hoc decision boundaries for making interim group sequential decisions that stop the trial early. Beyond the discussion of the particular study, we review more general considerations of using a decision theoretic approach for clinical trial design and summarize some of the reasons why such approaches are not commonly used. Copyright © 2017 John Wiley & Sons, Ltd.
Combined effect of therapeutic strategies for bleeding injury on early survival, transfusion needs and correction of coagulopathy
Authors: Balvers K , van Dieren S , Baksaas-Aasen K , Gaarder C , Brohi K , Eaglestone S , Stanworth S , Johansson P I , Ostrowski S R , Stensballe J , Maegele M , Goslings J C , Juffermans N P , Bergman R , Naess P A , Kolstadbråten K M , Rourke C , Gall L , Curry N , Stürmer E K , Schäfer N , Driessen A , Orr A , Schubert A , Görlinger K , Harrison M , Buchanan J , Char A , Neble S , Sayel H
Published: January 2017

Background

The combined effects of balanced transfusion ratios and use of procoagulant and antifibrinolytic therapies on trauma-induced exsanguination are not known. The aim of this study was to investigate the combined effect of transfusion ratios, tranexamic acid and products containing fibrinogen on the outcome of injured patients with bleeding.

Methods

A prospective multicentre observational study was performed in six level 1 trauma centres. Injured patients who received at least 4 units of red blood cells (RBCs) were analysed and divided into groups receiving a low (less than 1 : 1) or high (1 or more : 1) ratio of plasma or platelets to RBCs, and in receipt or not of tranexamic acid or fibrinogen products (fibrinogen concentrates or cryoprecipitate). Logistic regression models were used to assess the effect of transfusion strategies on the outcomes ‘alive and free from massive transfusion’ (at least 10 units of RBCs in 24 h) and early ‘normalization of coagulopathy’ (defined as an international normalized ratio of 1·2 or less).

Results

A total of 385 injured patients with ongoing bleeding were included in the study. Strategies that were independently associated with an increased number of patients alive and without massive transfusion were a high platelet to RBC ratio (odds ratio (OR) 2·67, 95 per cent c.i. 1·24 to 5·77; P = 0·012), a high plasma to RBC ratio (OR 2·07, 1·03 to 4·13; P = 0·040) and treatment with tranexamic acid (OR 2·71, 1·29 to 5·71; P = 0·009). No strategies were associated with correction of coagulopathy.

Conclusion

A high platelet or plasma to RBC ratio, and use of tranexamic acid were associated with a decreased need for massive transfusion and increased survival in injured patients with bleeding. Early normalization of coagulopathy was not seen for any transfusion ratio, or for use of tranexamic acid or fibrinogen products.
Synthesis and Structural Studies of Cp* Rhodium and Cp* Iridium Complexes of Picolinic Hydrazine Ligand
Authors: Palepu Narasinga Rao , Kaminsky Werner , Kollipara Mohan Rao
Published: January 2017

A series of Cp*Rh and Cp*Ir complexes of picolinic hydrazine ligand are synthesized and characterized. Picolinic hydrazine has yielded only dinuclear complexes in the case of rhodium metal whereas both mono and dinuclear complexes with iridium metal. Iridium complexes are formed as quaternary salts by the migration of the N–H proton onto the adjacent amine group of the hydrazine after binding to the metal. Picolinic hydrazine acts as nitrogen and oxygen donor ligand in the form of bi and tetradentate bonding modes.
Mechanistic insight into nuclear receptor‐mediated regulation of bile acid metabolism and lipid homeostasis by grape seed procyanidin extract (GSPE)
Authors: Downing Laura E. , Edgar Daniel , Ellison Patricia A. , Ricketts Marie‐Louise
Published: January 2017

Dietary procyanidins have emerged as important bioactive components that regulate various metabolic pathways to maintain homeostasis. Grape seed procyanidin extract (GSPE), in particular, has demonstrated regulatory effects on bile acid and lipid metabolism in vivo. While numerous studies in rodent models have shown the potent hypolipidemic action of grape seed extracts, human studies have shown inconsistent results. This review will focus on the molecular mechanisms underlying the hypolipidemic actions of GSPE identified to date, specifically highlighting the effects exerted via nuclear receptors. Such evidence may provide avenues for future research in human subjects with GSPE as a therapeutic treatment for the prevention and amelioration of the metabolic syndrome and cardiovascular disease.
Optimization of the Reaction Conditions for Catalytic Fast Pyrolysis of Pretreated Lignin over Zeolite for the Production of Phenol
Authors: Ma Zhiqiang , Ghosh Ashim , Asthana Navinchandra , van Bokhoven Jeroen
Published: January 2017

The catalytic fast pyrolysis of lignin for the production of phenols over commercial zeolites was studied in‐depth. The results show that the production of phenols depended on several parameters, such as lignin pretreatment methods, pyrolysis temperature, zeolite structure and acidity, pyrolysis time, and feed‐to‐catalyst weight ratio. Lignin pretreatments had a significant influence on the liquid‐product distribution. Hydrogen chloride pretreatment of lignin increased the depolymerization of the lignin matrix, resulting in an increase of the liquid yield, as well as the phenol fraction. High temperature (e.g., 650 °C) and a fast heating rate (20 °C ms−1) were required to depolymerize lignin and increase the yield of liquid products, and large‐pore‐size zeolites (e.g., FAU) with Si/Al of approximately 15 favored the formation of phenols. A long pyrolysis time (20 s) was also beneficial for phenol to desorb from the catalyst. The medium feed‐to‐catalyst weight ratio of approximately 1:1 prevented further conversion of phenols to deoxygenated products such as aromatic hydrocarbons (benzene, toluene, and xylene).
Hydrogen Purification Using Polybenzimidazole Mixed‐Matrix Membranes with Stabilized Palladium Nanoparticles
Authors: Suhaimi Hani Shazwani Mohd , Leo Choe Peng , Ahmad Abdul Latif
Published: January 2017

Palladium (Pd) nanoparticles stabilized by polyethylene glycol were incorporated into polybenzimidazole (PBI) to form a mixed‐matrix membrane (MMM) for hydrogen (H2) purification. Energy dispersive X‐ray results confirmed the existence of Pd nanoparticles in the PBI matrix. These dense membranes showed a homogeneously dispersed morphology in scanning electron microscope images that proves the excellent interphase affinity between PBI matrix and Pd nanoparticles. Unlike Pd membranes, the PBI(Pd) MMMs interact with H2 starting from a low temperature as indicated in temperature‐programmed reduction analysis. At elevated operating temperature, the PBI(Pd) MMM exhibited a higher selectivity compared to the neat PBI membrane. The PBI(Pd) MMM also surpassed the Robeson plot which represents the permeability/selectivity trade‐off.
The chemometrics revolution re‐examined
Authors: Brown Steven
Published: January 2017

When chemometrics began as a field, what is considered chemometrics and how chemometrics relates to neighboring fields all are issues that continue to impact the field today. This review discusses early efforts to create the new field of chemometrics and considers how these efforts continue to shape the field today. The review points out the need for change in some long‐established practices in chemometrics to keep the field strong in the face of rapid changes in data analysis and in chemical instrumentation.
Breaking the Gordian Knot in the Structural Chemistry of Polyoxometalates: Copper(II)–Oxo/Hydroxo Clusters
Authors: Kondinski Aleksandar , Monakhov Kirill Yu.
Published: January 2017

This Concept article provides insights into the molecular design and construction aspects of polyoxocuprates (POCus), an emerging class of polyoxometalate (POM)‐like architectures featuring low‐to‐high nuclearity copper(II)–oxo/hydroxo skeletons. POCus have been identified to adopt the structural principles of classical POMs consisting of early transition metals. Their potential to afford motifs of the noble‐metal‐based POMs is exploited. “Cross‐structural topological transformation” is introduced to generalize skeletal relationships between POCus and POMs. The study opens up strategies toward the brand‐new structural chemistry of POCus with relevance to homogeneous photocatalysis, medicinal chemistry, molecular magnetism, and quantum computing.
Homo‐C‐nucleoside analogs IV. Synthesis of 4‐(2,5‐anhydro‐D‐altro‐pentitol‐1‐yl)‐2‐phenyl‐2H‐1,2,3‐triazole homo‐C‐nucleoside. CD assignment of the absolute configuration of the carbon bridge
Authors: Sallam Mohammed A.E.
Published: January 2017

Dehydrative cyclization of 4‐(D‐altro‐pentitol‐1‐yl)2‐phenyl‐2H‐1,2,3‐triazole in basic medium with one moler equivalent of p‐toluene sulfonyl chloride in pyridine solution gave the homo‐C‐nucleoside 4‐(2,5‐anhydro‐D‐altro‐1‐yl)‐2‐phenyl‐2H‐1,2,3‐triazole. The structure and anomeric configuration was determined by acylation, nuclear magnetic resonance (NMR), and mass spectroscopy. The stereochemistry at the carbon bridge of homo‐C‐nucleoside 2‐phenyl‐2H‐1,2,3‐triazoles was determined by circular dichroism (CD) spectroscopy.
A cutting edge solution to monitor formation damage due to scale deposition: Application to oil recovery
Authors: Ahmadi Mohammad Ali , Mohammadzadeh Omidreza , Zendehboudi Sohrab
Published: January 2017

One of the detrimental issues in upstream oil industry is permeability impairment in oil reservoirs. The permeability may be reduced because of scale deposition originated from injected water incompatibility with the in‐situ water. To tackle this issue and monitor permeability impairment owing to scale deposition, an inventive evolutionary approach of Artificial Neural Network (ANN) is utilized which is based on the bio‐inspired science. This approach is optimized by various optimization algorithms which provide a high‐precision decision‐making process with low uncertainty associated with the interconnected weights of the developed neural network model. The constructed intelligent approaches are evaluated using extensive experimental data from the open literature. Moreover, two regression models are developed to highlight the robustness and precision of the addressed techniques. For model validation, the predictions obtained from the smart technique as well as the regression method are compared with the formation damage experimental data. Based on various performance criteria, it was obtained that the predictions from the optimized genetic algorithm have infinitesimal average relative and absolute deviation from the experimental data (< 0.1 %). The results obtained in the current research prove that implication of HGAPSO‐ANN in monitoring of formation damage associated with scale deposition in porous media results in reliable estimation of permeability impairment. This can result in designing a more reliable reservoir simulation model that captures the permeability impairment due to scale deposition, hence providing thorough action plans for developing EOR technologies that may cause scale deposition‐related formation damage.
Next‐generation sequencing of liquid‐based cytology non–small cell lung cancer samples
Authors: Reynolds Jordan P. , Zhou Yaolin , Jakubowski Maureen A. , Wang Zhen , Brainard Jennifer A. , Klein Roger D. , Farver Carol F. , Almeida Francisco A. , Cheng Yu‐Wei
Published: January 2017

BACKGROUND

The detection of mutated epidermal growth factor receptor (EGFR) in non–small cell lung cancer (NSCLC) with residual cell pellets derived from liquid‐based cytology (LBC) samples (eg, endoscopic ultrasound–guided fine‐needle aspiration) has been validated with allele‐specific polymerase chain reaction. The aim of this study was to validate next‐generation sequencing (NGS) technology for detecting gene mutations with residual cell pellets from LBC.

METHODS

Archived DNA extracted from LBC samples of adenocarcinoma stored in PreservCyt with a known EGFR mutation status was retrieved. Genomic DNA was multiplex‐amplified and enriched with Ion AmpliSeq Cancer Hotspot Panel v2 chemistry and the OneTouch 2 instrument; this was followed by semiconductor sequencing on the Ion Personal Genome Machine platform. The mutation hotspots of 6 NSCLC‐related genes (BRAF, EGFR, ERBB2, KRAS, MET, and phosphatidylinositol‐4,5‐bisphosphate 3‐kinase catalytic subunit α [PIK3CA]) were analyzed with NextGENe and Torrent Suite bioinformatics tools.

RESULTS

The commonly identified EGFR sequence changes, including 4 L858R mutations, 3 exon 19 deletions, and 1 exon 20 insertion, were in 100% concordance between the assay platforms. Less common NSCLC variants were also found in the mutation hotspots of ERBB2, KRAS, MET, and PIK3CA genes.

CONCLUSIONS

NSCLC mutation analysis using NGS can be successfully performed on residual cell pellets derived from LBC samples. This approach allows the simultaneous examination of multiple mutation hotspots in a timely manner to improve patient care. Cancer Cytopathol 2017;125:178–187. © 2016 American Cancer Society.
Molecular Analysis of Gene Rearrangements and Mutations in Acute Leukemias and Myeloid Neoplasms
Authors: Sholl Lynette M. , Longtine Janina , Kuo Frank C.
Published: January 2017

A subset of acute leukemias and other myeloid neoplasms contains specific genetic alterations, many of which are associated with unique clinical and pathologic features. These alterations include chromosomal rearrangements leading to oncogenic fusion proteins or alteration of gene expression by juxtaposing oncogenes to enhancer elements, as well as mutations leading to aberrant activation of a variety of proteins critical to hematopoietic progenitor cell proliferation and differentiation. Molecular analysis is central to diagnosis and clinical management of leukemias, permitting genetic confirmation of a clinical and histologic impression, providing prognostic and predictive information, and facilitating detection of minimal residual disease. This unit will outline approaches to the molecular diagnosis of the most frequent and clinically relevant genetic alterations in acute leukemias and myeloid neoplasms. © 2017 by John Wiley & Sons, Inc.
A Simple Protoplast‐Based Method for Screening Potent Artificial miRNA for Maximal Gene Silencing in Arabidopsis
Authors: Zhang Nannan , Zhang Dandan , Li Jian‐Feng
Published: January 2017

The unpredictability of in planta silencing efficiency of artificial micro RNAs (amiRNAs) has greatly limited the application of the amiRNA technology in basic and applied plant research. This unit describes a simple and robust method called the epitope‐tagged protein‐based amiRNA (ETPamir) screen for identifying the most effective amiRNA for silencing a particular Arabidopsis gene. After selecting three to four amiRNA candidates designed by the WMD3 web server for the target gene, the silencing efficiencies of the amiRNA candidates can be compared by co‐expressing individual amiRNAs with the target mRNA encoding an epitope‐tagged target protein in Arabidopsis mesophyll protoplasts. By monitoring target protein levels through immunoblotting with commercial “anti‐tag” antibodies, the most potent amiRNA can be easily identified as the one with minimal target protein accumulation. This empirical method bypasses the complexity of amiRNA silencing mechanisms and the scarcity of plant specific antibodies, and can be applied to a broad range of plant species. © 2017 by John Wiley & Sons, Inc.
Immunization of Mice
Authors: Maira‐Litrán Tomás
Published: January 2017

The selection of an appropriate immunization strategy depends largely on the properties of an antigen, including its nature, purity, solubility, and availability. This unit describes the critical steps in the production of monoclonal and polyclonal antibodies against soluble molecules (such as proteins, peptides, polysaccharides, oligosaccharides, or hapten‐conjugate vaccines), complex antigens (such as whole pathogens or outer membrane vesicles), and antigens embedded in or eluted from gel matrix following electrophoresis. © 2017 by John Wiley & Sons, Inc.
Designer Drugs 2.0
Authors: Huestis MA , Tyndale RF
Published: January 2017

This “Designer Drugs 2.0” issue of Clinical Pharmacology & Therapeutics focuses on novel psychoactive substances, primarily cannabinoids and cathinones, and the repurposing of established psychoactive compounds (e.g., modafinil, psilocybin, lysergic acid diethylamide, and 3,4‐methylenedioxymethamphetamine) that simultaneously offer new pharmacotherapies and pose serious health problems. Novel psychoactive substances were initially used as potent tools to investigate endogenous neurotransmitter systems; for example, synthetic cannabinoids have much higher potency than Δ9‐tetrahydrocannabinol at the cannabinoid receptors. However, they are now being used illicitly as well as being tested for their efficacy in numerous clinical indications. Likewise, previously established psychoactive drugs are being repurposed as treatments for a wide variety of indications where currently approved medications are ineffective. This set of papers examines the arising problems associated with designer drugs (e.g., adverse events, psychosis, rapid new synthesis, abuse liability testing, internet sales, scheduling) as well as the potential therapeutic promises in areas as diverse as cognition enhancement, exercise‐mimetics, epilepsy, multiple sclerosis, and posttraumatic stress disorder.
Sputtering and amorphization of crystalline semiconductors by Nanodroplet Bombardment
Authors: Grustan‐Gutierrez Enric , Wei Chuqi , Wang Bingru , Lanza Mario
Published: January 2017

In this review we expose how Nanodroplet Bombardment of surfaces by charged particles produced through electrospray atomization offers unparalleled opportunities for surface engineering of chemically inert crystalline materials. The sputtering yields and rates are comparable or higher than reactive etching techniques and significantly higher than other physical sputtering systems. Moreover, bombardment can amorphatize a thin layer of the target. The imposed physical characteristics of the electrospray, droplet diameter, molecular mass of the spray, and kinetic energy will determine the sputtering and amorphization efficiency, and the topography of the processed target. Molecular dynamics studies have clarified the mechanisms of both processes; amorphous layers appear due to ultra‐fast quenching of melted target pools around the impact area while sputtering is driven by a combination of collision cascades, thermal evaporation, and, for large and fast projectiles, of hydrodynamic forces.
Melt crystallization of binary mixture of fatty acids as model biofuel
Authors: Yamamoto Takuji , Fujikawa Takuto , Okamoto Nobuyoshi , Itoh Kazuhiro , Maeda Kouji , Fukui Keisuke , Kuramochi Hidetoshi
Published: January 2017

To account for both the growth of solid layer and solute distribution in melt crystallization, we proposed empirical equations involving heat and mass transfer at the solid‐liquid interface between the solid layer and melt. With the aim of separating saturated fatty acid as a solid phase from binary mixture of fatty acids as model biofuel, we performed melt crystallization by employing three different species of binary melts which contained triglyceride as unsaturated fatty acid, and myristic acid, palmitic acid, or stearic acid as saturated fatty acid, respectively. As a result, we confirmed the validity of the proposed equations under the varied crystallization conditions.