bluuebunny/crossref_metadata_2025_split huggingface dataset:
Chlorothiomethylation of Alkynes with HCl and Dimethyl Sulfoxide: An Efficient Approach to (E)‐α‐chloro‐β‐(methylthio)alkenes
Authors: Tong Hanqing. , Chen Cui , Liu Weibing. , Pan Yupeng. , Duan Linhai. 
Published: March 2019

AbstractSynthesis of (E)‐chlorovinyl methylsulfanes via chlorothiomethylation of alkynes with HCl and dimethyl sulfoxide (DMSO) under metal‐free and oxidant‐free conditions has been reported. This methodology is rare, in which chlorovinyl methylsulfanes are constructed using chlorosulfanes rather than the combination of HCl and DMSO to react with alkynes. This procedure introduces a new application of DMSO, which is employed as a source of the SMe group to directly insert into the carbon‐carbon triple bond of alkynes. Additionally, the reaction shows a broad substrate scope, good functional group compatibility, and excellent regioselectivity.
Acylation of Arylamines with Triethylamine Derivatives in Combination with tert‐Butyl Hydroperoxide
Authors: Chen Cui , Liu Weibing. , Liu Bifu. , Zhou Peng , Tan Hua 
Published: March 2019

AbstractN‐acylation of arylamines with di‐ and trialkyl amines has been reported. This approach provides a general synthesis of aromatic amides by an alkyl transfer through cleavage of the C−N bond, and acts as a model for N‐dealkylations and N‐acylations. Additionally, the synthesis is a promising method towards amidation reactions, wherein di‐ and trialkyl amine derivatives are employed as sources of acyl carbon atoms and tert‐butyl hydroperoxide is employed as the oxygen source of the acyl group.
Hydroxymethylation of technical lignins from South American sources with potential use in phenolic resins
Authors: Taverna María Eugenia , Felissia Fernando , Area María Cristina , Estenoz Diana Alejandra , Nicolau Verónica Viviana 
Published: March 2019

ABSTRACTThis work investigates the valorization of sodium lignosulfonate, kraft, and organosolv lignins from South America. A detailed characterization of the lignins and their chemical modification by hydroxymethylation through its reaction with formaldehyde were performed. The characterization included measurements of moisture, ash, carbohydrate contents, elemental and thermogravimetric analysis, and functional groups, molar mass distributions by Fourier transform infrared spectroscopy, and size exclusion chromatography, respectively. Also, reactive aromatic hydrogens (HAr) were quantified by the measurement of phenolic hydroxyl groups (P‐OH) content by UV–Vis spectroscopy. The different initial formaldehyde/lignin weight ratios (0.07, 1.47), temperatures (40, 50, and 70 °C), and pHs (9, 11); and the following of hydroxymethylation reactions by UV–Vis spectroscopy were investigated. All lignins resulted attractive for the use as replacement of phenol in phenolic resins, but sodium lignosulfonate was the most appropriate due to its water solubility. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47712.
Effect of core–shell rubber toughening on mechanical, thermal, and morphological properties of poly(lactic acid)/multiwalled carbon nanotubes nanocomposites
Authors: Mat Desa Mohd Shaiful Zaidi , Hassan Azman , Arsad Agus , Arjmandi Reza 
Published: March 2019

ABSTRACTThe effect of core–shell rubber (CSR) toughening on mechanical and thermal properties of poly(lactic acid)/multiwalled carbon nanotubes (PLA/CNT) nanocomposites were investigated. The nanocomposites were prepared by direct melt blending method in a counter‐rotating twin‐screw extruder. The contents of CSR were varied between 5 and 20 wt % while the content of CNT was kept at 5 phr. The extruded samples were injection molded into the desired test specimens for mechanical and thermal properties analysis. The impact strength of PLA/CNT increased with increasing CSR content with concomitant decrease in tensile strength and modulus. Interestingly, the flexural strength increased at low CSR content before decreasing at 15 and 20% content. Differential scanning calorimetry analysis on the second heating cycle shows no crystallinity content for PLA/CNT and all CSR toughened PLA/CNT nanocomposites, while thermogravimetric analysis shows lower thermal degradation of all CSR toughened PLA/CNT as compared to PLA/CNT nanocomposite. This study reveals significant correlation between CSR loading with the mechanical and thermal properties of the nanocomposites. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2019,136, 47756.
Protective Effect Against Cancer of Antibodies to the Large Subunits of Both RNA Polymerases I and III in Scleroderma
Authors: Shah Ami A. , Laiho Marikki , Rosen Antony , Casciola‐Rosen Livia 
Published: March 2019

ObjectiveWhile compelling data suggest a cancer‐induced autoimmunity model in scleroderma patients with anti–RNA polymerase III large subunit (anti‐RPC155) antibodies, ~85% of these patients do not manifest cancer. This study was undertaken to determine whether additional autoantigens are targeted in anti‐RPC155–positive scleroderma patients without detectable cancer.MethodsThe study included 168 scleroderma patients with anti‐RPC155 antibodies (80 with a history of cancer and 88 with no cancer diagnosis after >5 years of follow‐up). Thirty‐five sera (17 from patients with cancer and 18 from patients without cancer) were randomly selected for autoantibody discovery using immunoprecipitation (IP). An ~194‐kd band was enriched in the subgroup without cancer; this was identified as RNA polymerase I large subunit (RPA194).ResultsRPA194 generated by in vitro transcription/translation was used for IPs performed on the entire cohort to test whether anti‐RPA194 was enriched among anti‐RPC155–positive patients without cancer. Anti‐RPA194 antibodies were significantly more common in the group without cancer (16 [18.2%] of 88) than in the group with cancer (3 [3.8%] of 80) (P = 0.003). Patients with both anti‐RPA194 and anti‐RPC155 were significantly less likely to have severe gastrointestinal disease than patients with anti‐RPC155 only (26.3% versus 51.0%; P = 0.043).ConclusionAnti‐RPA194 antibodies are enriched in anti‐RPC155–positive scleroderma patients without cancer. Since somatic mutations in the gene encoding RPC155 in cancer in scleroderma patients appears to play a role in immune response initiation against RPC155 in those patients, these data raise the possibility that the development of immune responses to both RPC155 and RPA194 may influence clinical cancer emergence. Further study is required to define whether different autoantibody combinations have utility as tools for cancer risk stratification in scleroderma.
The association between prenatal alcohol exposure and protein expression in human placenta
Authors: Holbrook Bradley D. , Davies Suzy , Cano Sandra , Shrestha Shikhar , Jantzie Lauren L. , Rayburn William F. , Bakhireva Ludmila N. , Savage Daniel D. 
Published: March 2019

BackgroundThe need for earlier recognition of children at risk for neurobehavioral problems associated with prenatal ethanol exposure (PAE) has prompted investigations of biomarkers prognostic for altered fetal development. Here, we examined whether PAE alters the expression of angiogenesis‐related proteins and cytokines in human placenta in subjects from an Ethanol, Neurodevelopment, Infant and Child Health prospective cohort.MethodsPAE was ascertained by screening questionnaires, Time‐line Follow‐back interviews and a panel of ethanol biomarkers at two study visits. After delivery, placental tissue samples were collected for protein analysis.ResultsNo significant differences in the prevalence of substance use, demographic or medical characteristics were observed between the No PAE and PAE groups. PAE was associated with significant reductions in placental expression of VEGFR2 and annexin‐A4, while the levels of VEGFR1 and CCM‐3 trended downward. A trend toward higher expression of the cytokines TNF‐α and IL‐13 was also observed in the PAE group. Receiver operating characteristic analyses of the data demonstrated a moderate‐to‐high degree of diagnostic accuracy for individual placental proteins. Combinations of proteins substantially increased their ability to differentiate between PAE and No PAE subjects.ConclusionsThese results establish the feasibility of harvesting placental tissue for protein analyses of PAE in a prospective manner. In addition, given the importance of vascular remodeling in both placenta and developing brain, the role of angiogenic and cytokine proteins in this process warrants further investigation for their utility for predicting alterations in brain development, as well as their mechanistic role in PAE‐induced pathology.
Clinical value of additional resection of a margin-positive distal bile duct in perihilar cholangiocarcinoma
Authors: Otsuka S , Ebata T , Yokoyama Y , Mizuno T , Tsukahara T , Shimoyama Y , Ando M , Nagino M 
Published: March 2019

Abstract

Background
Little is known about the effect of additional resection for a frozen-section-positive distal bile duct margin (DM) in perihilar cholangiocarcinoma.

Methods
Patients who underwent surgical resection for perihilar cholangiocarcinoma between 2001 and 2015 were analysed retrospectively, focusing on the DM.

Results
Of 558 consecutive patients who underwent frozen-section examination for a DM, 74 (13·3 per cent) had a frozen-section-positive DM with invasive cancer or carcinoma in situ. Eventually, 53 patients underwent additional resection (bile duct resection in 44 and pancreatoduodenectomy in 9), whereas the remaining 21 patients did not. Ultimately, R0 resection was achieved in 30 of the 53 patients (57 per cent). No patient who underwent additional resection died from surgical complications. The 44 patients with additional bile duct resection had a 5-year overall survival rate of 31 per cent. Overall survival of the nine patients who had pancreatoduodenectomy was better, with a 10-year rate of 67 per cent. Survival of the 21 patients without additional resection was dismal: all died within 5 years. Multivariable analyses identified nodal status and additional resection as independent prognostic factors (lymph node metastasis: hazard ratio (HR) 2·26, 95 per cent c.i. 1·26 to 4·07; bile duct resection versus no additional resection: HR 0·32, 0·17 to 0·60; pancreatoduodenectomy versus no additional resection: HR 0·08, 0·02 to 0·29).

Conclusion
Additional resection for frozen-section-positive DM in perihilar cholangiocarcinoma frequently yields R0 margins. It offers a better chance of long-term survival, and thus should be performed in carefully selected patients.
Rituximab maintenance overcomes the negative prognostic factor of obesity in CLL: Subgroup analysis of the international randomized AGMT CLL‐8a mabtenance trial
Authors: Egle Alexander , Melchardt Thomas , Obrtlíková Petra , Smolej Lukáš , Kozák Tomáš , Steurer Michael , Andel Johannes , Burgstaller Sonja , Mikušková Eva , Gercheva Liana , Nösslinger Thomas , Papajík Tomáš , Ladická Miriam , Girschikofsky Michael , Hrubiško Mikuláš , Jäger Ulrich , Voskova Daniela , Pecherstorfer Martin , Králiková Eva , Burcoveanu Christina , Spasov Emil , Petzer Andreas , Mihaylov Georgi , Raynov Julian , Oexle Horst , Zabernigg August , Flochová Emília , Palášthy Stanislav , Stehlíková Olga , Doubek Michael , Altenhofer Petra , Weiss Lukas , Magnes Teresa , Pleyer Lisa , Klingler Anton , Mayer Jiří , Greil Richard 
Published: March 2019

AbstractNo data are available regarding obesity and outcome in Chronic Lymphocytic Leukemia (CLL). We analyzed 263 patients from the AGMT CLL‐8a Mabtenance trial for the impact of obesity. The trial included patients after rituximab‐containing induction treatment in first or second line that had achieved at least a PR. A randomization to rituximab maintenance treatment (375 mg/m2 q3 months for 2 years) vs observation was performed. In this cohort 22% of the patients (58/263) were classified as obese. The baseline response to induction treatment was inferior in obese patients with a lower CR rate (43.1% vs 60.5% in obese vs non‐obese, P = 0.018) and with a lower rate of patients achieving MRD negativity after chemoimmunotherapy induction treatment (19.6% vs 35.8%, P = 0.02). The PFS outcome of obese patients was significantly worse in the observation group of the trial (24 vs 39 months median PFS, P = 0.03). However, in the rituximab maintenance group the outcome for obese vs non‐obese was not different (P = 0.4). In summary, obesity was overall associated with a worse outcome of chemoimmunotherapy induction. However, rituximab maintenance treatment seems to be able to overcome this negative effect.
Genotype‐phenotype correlation in 99 familial adenomatous polyposis patients: A prospective prevention protocol
Authors: de Oliveira Junea C. , Viana Danilo V. , Zanardo Cleyton , Santos Erika M. M. , de Paula André E. , Palmero Edenir I. , Rossi Benedito M. 
Published: March 2019

AbstractBackgroundFamilial adenomatous polyposis (FAP) is a syndrome caused by germline pathogenic variants in the tumor suppressor gene adenomatous polyposis coli (APC). Identification of APC pathogenic variants sites and the genotype‐phenotype correlation are important for characterizing, monitoring, and treating members of affected families. The aim of this study was to correlate genotype‐phenotype of Brazilian individuals carrying APC pathogenic germline variants and that have FAP.MethodsThe polyposis phenotype of 99 individuals from 35 families between July 2013 and December 2014 were prospectively evaluated based on the InSIGHT polyposis staging classification. Seven extra‐colonic manifestations were assessed and the clinical manifestations correlated with the APC genotype.ResultsThe age of the study participants ranged from 12 to 67 years (median of 29 years). Twenty‐six APC pathogenic variants were identified. Fifty‐five cases harbored nonsense pathogenic variants (55.6%). Frameshift alterations were noted in 39 cases (39.4%). Aberrant splicing was noted in 1 case (1%). Rearrangements were observed in 3 cases (3%). An association between nonsense variants and rearrangement was noted in 1 case (1%). The genotype‐phenotype correlation analysis led the identification of classic FAP in 94 cases (94.9%). Profuse polyposis was identified in 5 cases (5.1%). Thirty‐six cases were diagnosed with cancer of which 29 cases (80.6%) were colorectal cancer, 1 case (2.7%) was brain cancer, 4 cases (11.2%) were papillary thyroid cancer, and 2 cases (5.5%) were stomach cancer. The extra‐colonic manifestations included 9 individuals with desmoids tumors, 10 with osteomas, and 9 with congenital hypertrophy of the retinal pigment epithelium.ConclusionsThe genotype‐phenotype correlation in Brazilian individuals with FAP revealed specific findings not previously reported for other cohorts, demonstrating the relevance of knowledge regarding the variable pathogenic variants and clinical presentation in different populations for adequate individual clinical management of patients harboring this medical condition.
Optimizing Microwave‐Assisted Extraction Conditions to Obtain Phenolic‐Rich Extract from Chromolaena odorata Leaves
Authors: Alara Oluwaseun Ruth , Abdurahman Nour Hamid , Abdul Mudalip Siti Kholijah 
Published: March 2019

AbstractPhenolic compounds are secondary metabolites that are mainly responsible for different pharmacological activities of plant extracts. In this study, microwave‐assisted extraction (MAE) variables were optimized for the extraction of phenolic compounds from Chromolaena odorata leaves by using a Box‐Behnken design of response surface methodology. The concentration of polyphenols and functional characteristics of the extracts were identified by using liquid chromatography quadrupolar time‐of‐flight mass spectrometry and FTIR analyses, respectively. The obtained results indicated the MAE conditions for the optimal recoveries of the total phenolic content and total flavonoid content from C. odorata leaves. The results reveal that the C. odorata leaf is enriched with phenolic compounds.
End‐to‐end quantitative analysis modeling of near‐infrared spectroscopy based on convolutional neural network
Authors: Chen Yuan‐Yuan , Wang Zhi‐Bin 
Published: March 2019

AbstractDuring the near‐infrared spectroscopy analysis process, modeling the quantitative relationship between the collected spectral information and target components is an important procedure. Before using the traditional modeling methods, it is often necessary to select the most featured wavelengths and eliminate those uninformative wavelengths. However, the wavelength selection algorithms can not only increase the model complexity but also may contain some adjustable parameters, which need the users to have more expertise knowledge and experiences. To solve this problem, this paper proposed a novel end‐to‐end quantitative analysis modeling method for near‐infrared spectroscopy based on convolutional neural network (CNN), which directly takes the whole range of collected raw spectral information as input without wavelength selection. The public corn NIR dataset was taken as example to validate the efficiency of proposed method. The experimental results showed that, firstly, if all the whole range of raw spectral information was taken as the input of modeling, the generalized performance of CNN outperforms the traditional methods, and the difference is statistically significant; secondly, if the traditional methods were combined with wavelength selection algorithms, their generalized performances were similar to CNN model; there is no statistical difference. The results indicated that applying the deep learning methods (take CNN as representative) to establish the quantitative analysis model of near‐infrared spectroscopy is easy to use and has more potential popularize values.
Magnesium Aldimines Prepared by Addition of Organomagnesium Halides to 2,4,6‐Trichlorophenyl Isocyanide: Synthesis of 1,2‐Dicarbonyl Derivatives
Authors: Schwärzer Kuno , Bellan Andreas , Zöschg Maximilian , Karaghiosoff Konstantin , Knochel Paul 
Published: March 2019

AbstractThe selective addition of organomagnesium reagents to 2,4,6‐trichlorophenyl isocyanide leading to magnesiated aldimines is reported. These aldimines react with Weinreb amides, ketones, or carbonates to provide the corresponding carbonyl derivatives after acidic cleavage. This allows for an efficient synthesis of 1,2‐dicarbonyl compounds and α‐hydroxy ketones.
Linear mode regression with covariate measurement error
Authors: Li Xiang , Huang Xianzheng 
Published: March 2019

AbstractWe consider estimating the mode of a response given an error‐prone covariate. It is shown that ignoring measurement error typically leads to inconsistent inference for the conditional mode of the response given the true covariate, as well as misleading inference for regression coefficients in the conditional mode model. To account for measurement error, we first employ the Monte Carlo corrected score method (Novick & Stefanski, 2002) to obtain an unbiased score function based on which the regression coefficients can be estimated consistently. To relax the normality assumption on measurement error this method requires, we propose another method where deconvoluting kernels are used to construct an objective function that is maximized to obtain consistent estimators of the regression coefficients. Besides rigorous investigation on asymptotic properties of the new estimators, we study their finite sample performance via extensive simulation experiments, and find that the proposed methods substantially outperform a naive inference method that ignores measurement error. The Canadian Journal of Statistics 47: 262–280; 2019 © 2019 Statistical Society of Canada
Mer‐Ir(ppy)3 to Fac‐Ir(ppy)3 Photoisomerization
Authors: Escudero Daniel 
Published: March 2019

AbstractIn this contribution a detailed mechanistic investigation of mer‐to‐fac photoisomerization occurring in Ir(ppy)3 (ppy=2‐phenylpyridine) is presented. Facial/meridional stereoisomerism in tris‐bidentate Ir(III) complexes strongly determines their photophysical properties and thereby their efficiency and stability within a phosphorescence‐based organic light‐emitting diode (PhOLED) device. Double‐hybrid density functional theory (DFT) calculations are performed herein to identify the photoactive species involved in the photoisomerization reaction and to assess its kinetic and thermodynamic feasibility at room temperature. These investigations highlight the protagonistic role of a non‐previously described 3MC (triplet metal‐centred) state bearing one stretched trans Ir–N position. Finally, and in view of the computed evidences, phosphor design strategies to prevent photoisomerization are proposed.
Successive Photoswitching and Derivatization Effects in Photochromic Dithienylethene‐Based Coordination Cages
Authors: Li Ru‐Jin , Han Muxin , Tessarolo Jacopo , Holstein Julian J. , Lübben Jens , Dittrich Birger , Volkmann Christian , Finze Maik , Jenne Carsten , Clever Guido H. 
Published: March 2019

AbstractA new series of [Pd2(L)4] cages based on photochromic dithienylethene (DTE) ligands allowed us to gain insight into the successive photoswitching of multiple DTE moieties in a confined metallo‐supramolecular assembly. Three new X‐ray structures of [Pd2(o‐L4)4], [Pd2(o‐L1)2(c‐L1)2] and [Pd2(c‐L1)4] (o‐L and c‐L = open and closed forms of DTE ligands, respectively) were obtained. The structures deliver snapshots of three different combinations of DTE photoisomeric states within the cage, facilitating a comparison of the all‐open with the all‐closed, and most notably, an intermediate form where open and closed switches co‐exist in the same cage. Moreover, a series of spherical anionic borate clusters was introduced in order to study their roles in the light‐controllable host–guest chemistry. The binding guests show higher affinities with the flexible open cage [Pd2(o‐L1)4] than with the rigid closed cage [Pd2(c‐L1)4]. For the [B12F12]2− guest, thermodynamic data obtained from NMR experiments was compared to results from isothermal titration calorimetry (ITC).
New sinusoidal oscillator configurations using operational transresistance amplifier
Authors: Komanapalli Gurumurthy , Pandey Rajeshwari , Pandey Neeta 
Published: March 2019

SummaryThe objective of this brief is to introduce four new structures of electronically tunable sinusoidal oscillators (SOs) designed using operational transresistance amplifier (OTRA). Each of the proposed SO consists of forward path derived from a generic structure along with one/two OTRA‐based resistive gain stages or differentiator in its feedback path. All the proposed SOs enjoy independent tuning of the frequency of oscillation (FO) through resistors without affecting the condition of oscillation (CO). Further, all topologies are found to exhibit low fo sensitivities at all frequencies with respect to circuit parameters, and the second topology is capable of achieving very low frequencies (VLFs) using less RC component spread and provides linear tuning too. The fourth circuit provides quadrature output. The proposed SOs have been successfully implemented and verified in 180‐nm CMOS technology node using ADE (analog design environment) tool Cadence Virtuoso. Both prelayout and postlayout simulation results have been included. To assess the oscillator prefabrication performances, Monte Carlo and process‐voltage‐temperature (PVT) analyses have been performed. The total harmonic distortion (THD) is observed to be less than 3.5%.