bluuebunny/crossref_metadata_2025_split huggingface dataset:
Optimization of Reactive Dividing‐Wall Distillation Column for Ethyl t‐Butyl Ether Synthesis
Authors: Kaur Jasdeep , Sangal Vikas K. 
Published: February 2018

AbstractEthyl t‐butyl ether (ETBE) was synthesized via reaction of ethanol and isobutene by means of a reactive dividing‐wall distillation column (RDWC). The RDWC was simulated using the RADFRAC model of Aspen Plus. Multi‐response optimization by response surface methodology (RSM) with desirability function approach was applied for maximizing product purities and minimizing energy requirements and CO2 emissions simultaneously with a constraint that the difference in pressure drop across the dividing wall should be zero. The prediction from the RSM optimization agrees well with the simulation. The optimized RDWC provided an excellent purity of 99.99 mol % of the product ETBE with about one‐third reduction in energy requirements and CO2 emissions as compared to reactive distillation.
Diazonium Grafting Control through a Redox Cross‐Reaction: Elucidation of the Mechanism Involved when using 2,2‐Diphenylpicrylhydrazyl as an Inhibitor
Authors: López Isidoro , Cesbron Marius , Levillain Eric , Breton Tony 
Published: February 2018

AbstractInvestigation into the mechanism involved in the control of layer growth through the reduction of diazonium salts by using 2,2‐diphenylpicrylhydrazyl (DPPH). This approach, previously assumed to be based on the radical capture of highly reactive aryl intermediates via the scavenging activity of DPPH, actually rests on redox cross reactions involving its electro‐reduced form. A numerical approach was developed to model the proposed processes, involving a redox reaction between diazonium cations and the reduced species of DPPH as a central step. Extension of this approach was validated by using substituted benzoquinones instead of DPPH, leading to good control of the radical polymerization to give sub‐monolayer surface coverage. Modulation of the surface coverage can be obtained by adjusting the concentration of the redox mediator and a near‐monolayer can be prepared in this way. The difference in formal redox potential between the diazonium salt and the electro‐reducible mediator was identified as a key parameter, and could be exploited to generalize the grafting control.
Oxygen and Nitrogen Co‐enriched Sustainable Porous Carbon Hollow Microspheres from Sodium Lignosulfonate for Supercapacitors with High Volumetric Energy Densities
Authors: Pang Jie , Zhang Wen‐Feng , Zhang Jin‐Liang , Zhang Hui‐Min , Cao Gao‐Ping , Han Min‐Fang , Yang Yu‐Sheng 
Published: February 2018

AbstractOxygen and nitrogen co‐enriched hierarchical porous carbon hollow microspheres are synthesized by using biomass‐derivative sodium lignosulfonate as a feedstock through a facile and scalable process. This four‐step synthesis process involves spray drying, thermal stabilization, carbonization, and post nitric acid modification. The as‐obtained carbon exhibits a moderate but efficient porosity (specific surface area of 991 m2 g−1, total pore volume of 0.75 cm3 g−1), small particle size of 0.2–5 μm, high electrode density of 0.45 g cm−3, and abundant surface oxygen/nitrogen species (13.12 at.%/0.97 at.%). Its electrochemical performance is evaluated by assembling into supercapacitors in 7 M KOH electrolyte. The three‐electrode cell presents a high gravimetric capacitance of 284 F g−1 at 0.1 A g−1 and good rate capability of 43.6 % at 20 A g−1. While the two‐electrode cell gives an impressive volumetric capacitance of 21.2 F cm−3 at 0.1 A g−1, marvelous volumetric energy density of 2.9 Wh L−1 at 11.3 W L−1, and remarkable cycling stability of 93.4 % capacitance retention after 10000 cycles, which is superior or comparable to that of commercial activated carbon.
A Functional Platform for the Detection of JWH‐073 as a Model for Synthetic Cannabinoids
Authors: Sengel Tulay Yilmaz , Celik Emine Guler , Aydogan Cansu , Gumus Zinar Pinar , Ilktac Raif , Celikbas Eda , Ciftci Mustafa , Aldemir Ebru , Coskunol Hakan , Timur Suna , Yagci Yusuf 
Published: February 2018

AbstractDuring the last decade, progress has been made in the on‐site detection of abused drug use. Herein, we present an electrochemical biosensor for the detection of one of the synthetic cannabinoids (SCs), JWH‐073, using poly (methyl methacrylate) (PMMA) hyperbranched copolymer (HBC) as a base coating and antibody molecules to bind the JWH‐073 to the surface. Modification of the surface is proved with various techniques such as differential pulse voltammetry, cyclic voltammetry, and electrochemical impedance spectrometry. The limit of detection and linearity (in logarithmic scale) for JWH‐073 were found to be 31.87 ng/mL and 25–500 ng/mL, respectively. The selectivity of the proposed biosensor was also tested in the presence of interfering molecules and the response was much higher for JWH‐073 in all measurements. In the final part of the study, synthetic urine was tested with the device and the relative standard deviation value was calculated to be less than 5.0 %. The confirmation of data from the resulting bio‐platform was performed via LC‐QTOF/MS. This work is the first of its kind, a novel, rapid, cost‐effective sensing platform for the detection of the SC.
Correlation and redundancy on machine learning performance for chemical databases
Authors: Li Hongzhi , Li Wenze , Pan Xuefeng , Huang Jiaqi , Gao Ting , Hu LiHong , Li Hui , Lu Yinghua 
Published: February 2018

AbstractVariable reduction is an essential step for establishing a robust, accurate, and generalized machine learning model. Variable correlation and redundancy/total correlation are the primary considerations in many variable reduction methods given that they directly impact model performances. However, their effects vary from one class of databases to another. To clarify their effects on regression models on the basis of small chemical databases, a series of calculations are performed. Regression models are built on features with various correlation coefficients and redundancies by 4 machine learning methods: random forest, support vector machine, extreme learning machine, and multiple linear regression. The results suggest that the correlation is, as expected, closely related to the prediction accuracy; ie, generally, the features with large correlation coefficients regarding to response variables achieve better regression models than those with lower ones. However, for the redundancy, no trends on the performances of regression models are disclosed. This may indicate that for these chemical molecular databases, the redundancy might not be a primary concern.
Circularly Polarized Luminescence from Inorganic Materials: Encapsulating Guest Lanthanide Oxides in Chiral Silica Hosts
Authors: Sugimoto Masumi , Liu Xin‐Ling , Tsunega Seiji , Nakajima Erika , Abe Shunsuke , Nakashima Takuya , Kawai Tsuyoshi , Jin Ren‐Hua 
Published: February 2018

AbstractInvited for the cover of this issue is the group of Ren‐Hua Jin at the Kanagawa University and co‐workers at Nara Institute of Science and Technology. The image depicts lanthanide metals encapsulated within temperature‐resistant chiral silica emitting polarized light. Read the full text of the article at 10.1002/chem.201705862.
Promotion of a Reaction by Cooling: Stereoselective 1,2‐cis‐α‐Thioglycoconjugation by Thiol‐Ene Coupling at −80 °C
Authors: Eszenyi Dániel , Kelemen Viktor , Balogh Fanny , Bege Miklós , Csávás Magdolna , Herczegh Pál , Borbás Anikó 
Published: February 2018

AbstractThe photoinitiated thiol‐ene coupling reactions of 2‐substituted glycals were studied as a generally applicable strategy for stereoselective 1,2‐cis‐α‐thioconjugation. Although all glycals reacted with full α‐selectivity, the efficacy of the reactions varied in a broad range depending on their configuration and glycals bearing axial acetoxy substituents reacted with very low efficacy at room temperature. The study revealed that the reaction progress could be promoted by cooling and inhibited by heating. At −80 °C, the equilibrium of the rapidly reversible addition of the thiyl radical to alkenes is shifted almost completely toward products, leading to efficient addition reactions. By exploiting this unique temperature effect a series of α‐thio‐l‐fucosides, ‐d‐galactosides, and d‐GlcNAc derivatives were prepared with high efficacy and complete stereoselectivity.
Chemical engineering research synergies across scientific categories
Authors: Patience Gregory S. , Patience Christian A. , Bertrand François 
Published: February 2018

AbstractChemical engineers operate industrial plants, design reactors and equipment, manage capital projects, estimate costs, project earnings, and drive efficiency through innovation while maintaining rigorous safety standards. The undergraduate curriculum includes mathematics, physics, chemistry, mechanics, biology, and management, much of which is common with other engineering departments. However, chemical engineering research is more related to chemistry. Here, we show that chemical engineers cite journals in WoS’ chemical engineering category most, followed by physical chemistry, energy & fuels, multi‐disciplinary chemistry, environmental science, and multi‐disciplinary materials science. According to a bibliometric analysis, the major research poles include materials, biotechnology, catalysis, environment, and thermodynamics. The 5 top cited journals in 2012 were Ind. Eng. Chem. Res., J. Membrane Sci., Chem. Eng. Sci., J. Hazard. Mater., and J. Catal., which are not the journals with the highest impact factors of the category. Can. J. Chem. Eng. was ranked third among the 32 classical chemical engineering journals after AIChE J. and Chem. Eng. Sci. and with respect to the ratio of the number of citations accrued until August 2017 to the number of articles they published in 2012. Chinese researchers have authored more articles than any other nation and they co‐author research most with the USA and other Pacific Rim nations. Research collaborations between nations follow linguistic, geographical, and historical traditions.
Towards developing a meaningful grading system for cervical squamous cell carcinoma
Authors: McCluggage W Glenn 
Published: February 2018

AbstractCervical cancer is one of the commonest cancers worldwide, especially in developing countries. In early stage disease, a variety of pathological parameters are of prognostic value but currently this does not include tumour grade which, for a number of reasons, is of limited or no value in cervical squamous cell carcinomas. In a recent article in this journal, Jesinghaus and colleagues investigated a novel histopathological grading system based on tumour budding and cell nest size, which has been shown to outperform conventional grading systems for squamous cell carcinoma at several other sites such as lung, oral cavity, and oesophagus in terms of patient prognostication. They tested the prognostic value of this grading system in two independent cohorts of cervical squamous cell carcinoma. The grading system proved to be a highly effective, stage‐independent prognosticator in both cohorts with small cell nest size and high tumour budding indicative of a poor prognosis. It is hoped that the results of this study will be validated in additional independent larger cohorts and will act as an impetus for the development of a meaningful and easy‐to‐implement grading system for cervical squamous cell carcinoma. As comparable tumour budding/cell nest size‐based grading systems have been shown to be of prognostic value for squamous cell carcinomas at other sites, this shows the potential of these parameters to serve as the basis for a common grading system applicable to squamous cell carcinomas of different anatomic sites.
Lupus nephritis: low urinary DNase I levels reflect loss of renal DNase I and may be utilized as a biomarker of disease progression
Authors: Pedersen Hege L , Horvei Kjersti D , Thiyagarajan Dhivya , Norby Gudrun E , Seredkina Natalya , Moroni Gabriella , Eilertsen Gro Ø , Holdaas Hallvard , Strøm Erik H , Bakland Gunnstein , Meroni Pier‐Luigi , Rekvig Ole P 
Published: February 2018

AbstractRenal DNase I is lost in advanced stages of lupus nephritis. Here, we determined if loss of renal DNase I reflects a concurrent loss of urinary DNase I, and whether absence of urinary DNase I predicts disease progression. Mouse and human DNase I protein and DNase I endonuclease activity levels were determined by western blot, gel, and radial activity assays at different stages of the murine and human forms of the disease. Cellular localization of DNase I was analyzed by immunohistochemistry, immunofluorescence, confocal microscopy, and immunoelectron microscopy. We further compared DNase I levels in human native and transplanted kidneys to determine if the disease depended on autologous renal genes, or whether the nephritic process proceeded also in transplanted kidneys. The data indicate that reduced renal DNase I expression level relates to serious progression of lupus nephritis in murine, human native, and transplanted kidneys. Notably, silencing of renal DNase I correlated with loss of DNase I endonuclease activity in the urine samples. Thus, urinary DNase I levels may therefore be used as a marker of lupus nephritis disease progression and reduce the need for renal biopsies.
Spectroscopic and Hydrodynamic Characterisation of DNA‐Linked Gold Nanoparticle Dimers in Solution using Two‐Photon Photoluminescence
Authors: Midelet Johanna , El‐Sagheer Afaf H. , Brown Tom , Kanaras Antonios G. , Débarre Anne , Werts Martinus H. V. 
Published: February 2018

AbstractTwo‐photon photoluminescence (TPPL) emission spectra of DNA–gold nanoparticle (AuNP) monoconjugates and the corresponding DNA‐linked AuNP dimers are obtained by photon time‐of‐flight spectroscopy. This technique is combined with two‐photon photoluminescence fluctuation correlation spectroscopy (TPPL–FCS) to simultaneously monitor the optical and hydrodynamic behaviour of these nano‐assemblies in solution, with single‐particle sensitivity and microsecond temporal resolution. In this study, the AuNPs have an average core diameter of 12 nm, which renders their dark‐field plasmonic light scattering too weak for single‐particle imaging. Moreover, as a result of the lack of plasmonic coupling in the dimers, the optical extinction, scattering and photoluminescence spectra of the DNA–AuNP complexes are not sufficiently different to distinguish between monomers and dimers. The use of TPPL–FCS successfully addresses these bottlenecks and enables the distinction between AuNP monomers and AuNP dimers in solution by measurement of their hydrodynamic rotational and translational diffusion.
Formation Mechanism of Atmospheric Ammonium Bisulfate: Hydrogen‐Bond‐Promoted Nearly Barrierless Reactions of SO3 with NH3 and H2O
Authors: Chen Shunwei , Zhao Yanling , Zhang Ruiqin 
Published: February 2018

AbstractParticulate matter (PM) air pollution threatens the health of people and ecosystems worldwide. As the key component of PM, ammonium sulfate plays a critical role in the formation of aerosol particles; thus, there is an urgent need to know the detailed mechanisms for its formation in the atmosphere. Through a quantum chemistry study, we reveal a series of nearly barrierless reactions that may occur in clusters/droplets in the atmosphere leading to the formation of ammonium bisulfate (NH4HSO4), the precursor of ammonium sulfate. In this mechanism, NH4HSO4 is directly formed through one‐step reactions of SO3 with H2O and NH3 promoted by surrounding molecule(s) that substantially lower the reaction activation barrier to ≈0 kcal mol−1. The promoters of these reactions are found to be various common atmospheric molecules, such as water, ammonia, and sulfuric acid, which can form relatively strong hydrogen bonds with the reaction center. Our results suggest many more similar pathways that can be facilitated by other ambient molecules. Due to its one‐step and barrierless reaction characteristics and the great abundance of potential reactions, this mechanism has great implications on the formation of atmospheric ammonium sulfate as well as on the growth of aerosol particles.
Evaluation of the benefit and use of the new terminology in endometrial cytology reporting system
Authors: Shinagawa Akiko , Kurokawa Tetsuji , Yamamoto Makoto , Onuma Toshimichi , Tsuyoshi Hideaki , Chino Yoko , Iwasaki Kazumi , Mori Masaki , Imamura Yoshiaki , Yoshio Yoshida 
Published: February 2018

ObjectiveThe introduction and establishment of a new classification system for endometrial cytology, the “New Terminology in Endometrial Cytology (NTEMC) system,” which is based on the Bethesda System for uterine cervical cytology, has recently been reported. However, the clinical management for new categories in the NTEMC system, particularly atypical endometrial cells (ATEC), has not been clarified. The objective of the present study is to determine how the ATEC category should be treated and whether the introduction of the system has decreased the number of unnecessary endometrial biopsies.MethodsFifty‐nine cases were diagnosed as “suspicious positive” according to the three‐tier reporting (TTR) system, which was adopted in Japan. The specimens were re‐evaluated according to the NTEMC system. Thirty‐seven of the 59 patients underwent endometrial biopsy. We correlated the pathological diagnosis with the NTEMC system category.ResultsThe 59 cases were classified according to the NTEMC system as follows: 36 cases were classified as ATEC of undetermined significance (ATEC‐US), 21 cases were classified as ATEC for which atypical endometrial hyperplasia or worse cannot be excluded (ATEC‐A), and 2 cases were classified as endometrial hyperplasia. The ratio of atypical endometrial hyperplasia or malignancy in ATEC‐US category was significantly lower than that in ATEC‐A category. Fifteen cases in ATEC‐US category did not show atypical endometrial hyperplasia lesions or malignancy after 3 months.ConclusionsThese data suggest that patients with ATEC‐US results can be followed up for at least three months, and the introduction of the NTEMC system decreased the number of unnecessary endometrial biopsies.
Differential expression of various clones of estrogen receptor in cell block preparation of lung adenocarcinoma
Authors: Hakima Laleh , Schlesinger Kathie , Sunkara Jaya , Karabakhtsian Rouzan G. 
Published: February 2018

BackgroundWomen treated for breast cancer are at increased risk of developing pulmonary nodules which could represent new primary lung carcinomas or metastatic breast carcinoma. The FNA biopsy is frequently the first diagnostic choice in determining the primary site of the tumor. Estrogen receptor (ER) positivity in diagnostic tissue is generally used to favor breast over lung primary. However, the recent studies have shown a wide range of ER antibody cross reactivity with lung adenocarcinoma. We studied the frequency of ER expression in cytology samples of lung adenocarcinoma using antibodies to three different ER clones.MethodsCytology cell block preparations, including 22 lung FNAs and 19 malignant pleural effusions (PE) from 41 patients, with clinically documented primary lung adenocarcinomas were selected for this study. All cases were stained with monoclonal antibodies to ER clones 6F11 and 1D5. Twenty nine cases with remaining available material (15 FNA and 14 PE) were stained with a third antibody to ER clone SP1. The extent of ER nuclear staining was scored as 3+ (50%–100% of tumor cells), 2+ (11%–49%), and 1+ (≤10%).ResultsPositivity for ER‐6F11 clone was present in 4 of 22 lung FNAs (18.2%, 2+ staining). Two of the four 6F11 positive FNAs also co‐expressed ER‐1D5 (9.1%, 2+ staining). No immunoreactivity was observed for ER clones 6F11 and 1D5 in all 19 malignant PEs. In addition, none of the remaining 15 FNAs and 14 PEs showed immunoreactivity for ER‐SP1 clone.ConclusionsA small subset of pulmonary adenocarcinomas shows immunoreactivity for ER clones 6F11 and 1D5 in FNA samples (18.2% and 9.1%, respectively). The absence of immunoreactivity for ER‐SP1 clone indicates higher specificity of this clone in non‐breast tissue. The differential diagnostic value of all ER clones in malignant PEs appears to be secure. Larger studies are necessary to validate this observation.
Lessons learned from the 1‐hour post‐load glucose level during OGTT: Current screening recommendations for dysglycaemia should be revised
Authors: Bergman Michael , Jagannathan Ram , Buysschaert Martin , Pareek Manan , Olsen Michael H. , Nilsson Peter M. , Medina José Luis , Roth Jesse , Chetrit Angela , Groop Leif , Dankner Rachel 
Published: February 2018

AbstractThis perspective covers a novel area of research describing the inadequacies of current approaches for diagnosing dysglycaemia and proposes that the 1‐hour post‐load glucose level during the 75‐g oral glucose tolerance test may serve as a novel biomarker to detect dysglycaemia earlier than currently recommended screening criteria for glucose disorders. Considerable evidence suggests that a 1‐hour post‐load plasma glucose value ≥155 mg/dl (8.6 mmol/L) may identify individuals with reduced β‐cell function prior to progressing to prediabetes and diabetes and is highly predictive of those likely to progress to diabetes more than the HbA1c or 2‐hour post‐load glucose values. An elevated 1‐hour post‐load glucose level was a better predictor of type 2 diabetes than isolated 2‐hour post‐load levels in Indian, Japanese, and Israeli and Nordic populations. Furthermore, epidemiological studies have shown that a 1‐hour PG ≥155 mg/dl (8.6 mmol/L) predicted progression to diabetes as well as increased risk for microvascular disease and mortality when the 2‐hour level was <140 mg/dl (7.8 mmol/L). The risk of myocardial infarction or fatal ischemic heart disease was also greater among subjects with elevated 1‐hour glucose levels as were risks of retinopathy and peripheral vascular complications in a Swedish cohort. The authors believe that the considerable evidence base supports redefining current screening and diagnostic recommendations with the 1‐hour post‐load level. Measurement of the 1‐hour PG level would increase the likelihood of identifying a larger, high‐risk group with the additional practical advantage of potentially replacing the conventional 2‐hour oral glucose tolerance test making it more acceptable in a clinical setting.
Males prefer virgin females, even if parasitized, in the terrestrial isopod Armadillidium vulgare
Authors: Fortin Margot , Debenest Catherine , Souty‐Grosset Catherine , Richard Freddie‐Jeanne 
Published: February 2018

AbstractIn many species, males increase their reproductive success by choosing high‐quality females. In natural populations, they interact with both virgin and mated females, which can store sperm in their spermatheca. Therefore, males elaborate strategies to avoid sperm competition. In the terrestrial isopod Armadillidium vulgare, females can store sperm and produce several clutches. Moreover, this species can be parasitized by Wolbachia, which feminizes genetic males, transforming them into functional females. Our study compared attractiveness and mate choice when a male is exposed to both virgin and experienced females (i.e., females who have produced offspring and rested for 6 months), with or without Wolbachia. Our results revealed that males are more attracted to virgin females than experienced females, even if these virgin females are parasitized. Moreover, the chemical analysis highlighted different odors in females according to their reproductive and infection (Wolbachia‐free or vertically Wolbachia‐infected) status. Males attempted copulation more frequently and for longer with virgin females, even if Wolbachia‐infected, while experienced females refused further copulation. The evolutionary consequences of both male choice and female resistance on their fitness are discussed in this study.