bluuebunny/crossref_metadata_2025 huggingface dataset:
Reaction of arylhydrazines with diaryl ditellurides in the air: Insight into bimolecular homolytic substitution on tellurium via Aryl–Te bond cleavage
Authors: Yamamoto Yuki , Sato Fumiya , Kodama Shintaro , Nomoto Akihiro , Ogawa Akiya
Published: January 2019

The reactivity of diaryl ditelluride and diaryl telluride toward aryl radicals was studied in detail. Diphenyl ditelluride underwent a bimolecular homolytic substitution (SH2) reaction with a phenyl radical generated from phenylhydrazine in the air, to afford diphenyl telluride in excellent yield. Based on this diphenyl telluride synthesis, a one‐pot synthesis of unsymmetrical diaryl tellurides was developed by the SH2 reaction of in situ generated diphenyl telluride with arylhydrazines in the air. The selectivity of mono‐/di‐substitution and the reactivity of arylhydrazines depend on the nature of the substituents on the arylhydrazines, that is, electron‐donating or ‐withdrawing group.
Increased risk of oropharyngeal cancers mediated by oral human papillomavirus infection: Results from a Canadian study
Authors: Laprise Claudie , Madathil Sreenath Arekunnath , Schlecht Nicolas F. , Castonguay Geneviève , Soulières Denis , Nguyen‐Tan Phuc Felix , Allison Paul , Coutlée François , Hier Michael , Rousseau Marie‐Claude , Franco Eduardo L. , Nicolau Belinda
Published: January 2019

Background

This study aimed to estimate the extent to which oral sex behavior is associated with an increased risk of oropharyngeal cancers (OPCs), and how much of the association is mediated by oral human papillomavirus (HPV) infection.

Methods

We used data from a hospital‐based case‐control study conducted in Montreal, Canada. Information on oral sex behaviors was collected. Oral rinse and oral brush specimens were analyzed for HPV positivity and genotyping. Logistic regression estimated the odds ratios (OR) and 95% confidence intervals (CI) for the association between oral sex behaviors and OPC.

Results

Onset of oral sex practice at age 16 years or younger had an increased risk of OPCs relative to those with onset after age 30 years (OR = 2.98; 95% CI 1.37‐6.47). This association decreased (OR = 1.09; 95% CI 0.25‐4.71) when restricted to those positive for HPV.

Conclusions

Our results suggest that the association between oral sex and OPC seems mediated by oral HPV infection.
Timosaponin AIII inhibits metastasis of renal carcinoma cells through suppressing cathepsin C expression by AKT/miR‐129‐5p axis
Authors: Chiang Kuang‐Chung , Lai Chung‐Yu , Chiou Hui‐Ling , Lin Chia‐Liang , Chen Yong‐Syuan , Kao Shao‐Hsuan , Hsieh Yi‐Hsien
Published: January 2019

Timosaponin AIII (TSAIII) is a steroidal saponin that exerts anticancer activity on various cancer cells. In this study, we explore the effects of TSAIII on renal cell carcinoma (RCC) cells. Our findings show that TSAIII treatment (<8 μM) insignificantly influenced cell viability and cell cycle distribution of human RCC cell lines 786‐O, A‐498, and ACHN. Further observations revealed that TSAIII inhibited migration and invasion of 786‐O and A‐498 cells, as well as significantly decreased the production and expression of cathepsin C (CTSC) in both the cell types. Kinase cascade analysis exhibited that PI3K/AKT activation was inhibited, but PTEN expression was increased, in response to TSAIII treatments. Combining TSAIII and PI3K inhibitors, LY294002 synergically reduced the migration and invasion of 786‐O and A‐498 cells, as well as decreased the CTSC expression in both the cell types. We also observed that miR‐129‐5p bound to CTSC gene and suppressed the expression of CTSC and demonstrated that the miR‐129‐5p expression was synergically enhanced by TSAIII and LY294002. In addition, pretreatment with antago‐miR‐129‐5p significantly restored the CTSC expression and the migration and invasion of TSAIII‐treated 786‐O cells. In conclusion, our findings reveal that TSAIII inhibits the metastatic properties of RCC cells, contributing to the inhibition of PI3K/AKT and the increase of miR‐129‐5p and the subsequent downregulation of CTSC. This suggests that TSAIII has significant antimetastatic activity against RCC cells and may be beneficial to RCC treatments.
Adenoviral delivery of adiponectin ameliorates osteogenesis around implants in ovariectomized rats
Authors: Yin Guozhu , Liu Hanghang , Li Jiayang , Liu Yao , Liu Xian , Luo En
Published: January 2019

Background

Adiponectin (APN) has been reported to promote bone formation. However, it is difficult to utilize a conventional method that administers sufficient APN to the implant site. The present study investigated the efficacy of an APN transgene to accelerate the implant osseointegration in ovariectomized (OVX) rats.

Methods

In vitro, bone marrow stromal cells were transduced with reconstructed adenovirus (Ad‐APN‐EGFP) and osteoclast precursor RAW264.7 cells were co‐cultured with the conditioned medium secreted by transduced bone marrow stromal cells. Tartrate‐resistant acid phosphatase staining and bone slice resorption assay were performed to evaluate the activity of osteoclastogenesis. In vivo, Ad‐APN‐EGFP was administered into the bone defect prior to implant placement in OVX rats. At 7 and 28 days post implantation, the femurs were harvested and prepared for a real‐time reverse transcriptase‐polymerase chain reaction, hemotoxylin and eosin staining, immunohistochemical staining, micro‐computed tomography analysis and biomechanical testing.

Results

The results showed the formation and function of osteoclasts were significantly suppressed in vitro. Successful transgene expression was confirmed, and a significant increase of OCN, Runx2 and ALP expression was detected in the Ad‐APN‐EGFP group in vivo. Interestingly, we also found that the overexpression of APN decreased the expression level of potent adipogenic transcription factors such as PPARγ2 and C/EBP‐α. At 28 days after implantation, the Ad‐APN‐EGFP group revealed a significantly increased osseointegration and implant stability in OVX rats compared to the control groups (Ad‐EGFP and PBS groups).

Conclusions

APN via direct adenovirus‐mediated gene transfer could ameliorate osseointegration surrounding titanium implants in OVX‐related osteoporosis rats. Furthermore, it may be an effective strategy for promoting bone regeneration under osteoporotic conditions.
A New Multicomponent Synthetic Route to Hexahydropyrido[2,3‐d]pyrimidine Derivatives
Authors: Afrough Toktam , Bakavoli Mehdi , Eshghi Hossein
Published: January 2019

A new one‐pot multicomponent reaction of equimolar amounts of malononitrile and benzaldehyde in ethanol for the synthesis of hexahydropyrido[2,3‐d]pyrimidine derivatives through a sequence of Knoevenagel condensation, Michael addition, and Addition of Nucleophile, Ring Opening, and Ring Closure process is described.
Efficient gallium‐68 radiolabeling reaction of DOTA derivatives using a resonant‐type microwave reactor
Authors: Yagi Yusuke , Shimizu Yoichi , Arimitsu Kenji , Nakamoto Yuji , Higuchi Takahiro , Togashi Kaori , Kimura Hiroyuki
Published: January 2019

Gallium‐68 (68Ga, t1/2 = 68 min) can be easily obtained from a 68Ge/68Ga generator, and several such systems are commercially available. The use of positron emission tomography (PET) imaging using 68Ga‐labeled radiopharmaceuticals is expected to increase in both preclinical and clinical settings. However, the chelation between a 68Ga cation and the bifunctional macrocyclic chelates that are used for labeling bioactive substances, such as 1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetraacetic acid (DOTA), requires a relatively long reaction time and high temperature to achieve a high radiochemical yield. Previously, we reported on a novel resonant‐type microwave reactor that can be used for radiosynthesis and the usefulness of this reactor in the PET radiosynthesis of 18F. In the present study, the usefulness of this resonant‐type microwave reactor was evaluated for the radiolabeling of model macrocyclic chelates with 68Ga. As a result, microwave heating of resonant‐type microwave reactor notably improved the rate of the 68Ga labeling chelate reaction in a short time period of 2 minutes, compared with the use of a conventional heating method. Additionally, it was found that the use of this reactor made it possible to decrease the amount of precursors required in the reaction and to improve the molar activity of the labeled compounds.
Antimicrobial potential of haloalkaliphilic Nocardiopsis sp. AJ1 isolated from solar salterns in India
Authors: Adlin Jenifer John Selesteen Charles , Michaelbabu Mariavincent , Eswaramoorthy Thirumalaikumar Chinnadurai Lelin , Jeraldin Nisha Selva Raj , Uma Ganapathi , Citarasu Thavasimuthu
Published: January 2019

Antagonistic haloalkaliphilic Nocardiopsis sp. AJ1 (GenBank JX575136.1), isolated and identified from the saline soil of Kovalam solar salterns was able to produce antimicrobial secondary metabolites and effectively suppressed several bacterial and fungal pathogens. The metabolite extracted from ethyl acetate precipitation suppressed the bacterial and fungal pathogens to the range between 2.14 and 20.14 mm and also controlled the shrimp killer virus WSSV by 83% than the control and significantly (p < 0.05) differed. GC‐MS analysis revealed that, the ethyl acetate precipitation contains pyrrolo (1,2‐A(pyrazine‐1,4‐dione, hexahydro‐3‐(2‐methylpropyl)‐) and actinomycin C2. Non ribosomal peptide synthetase (NRPS) was amplified by PCR with the amplicon size of 750‐800 bp length and further predicted the secondary structure by Iterative Threading Assembly Refinement (I‐TASSER) bioinformatics approach. I‐TASSER prediction helped to find out the secondary, 3‐D structure, and ligand binding sites. The top ten modelling concluded that, the NRPS gene is closely similar to surfactin synthesizing gene, surfactin A synthetase C (SRFA‐C). The findings revealed that, the active compounds from the secondary metabolites effectively suppressed the pathogenic bacteria, fungi, and virus and useful to develop antimicrobials.
Bowel Ultrasound State of the Art: Grayscale and Doppler Ultrasound, Contrast Enhancement, and Elastography in Crohn Disease
Authors: Lu Cathy , Merrill Christina , Medellin Alexandra , Novak Kerri , Wilson Stephanie R.
Published: January 2019

Bowel ultrasound (US) is accurate for assessing bowel inflammation and complications in Crohn disease. Additionally, contrast‐enhanced US provides a quantitative, objective measurement of inflammatory activity in inflammatory bowel disease, and shear wave elastography predicts the stiffness of bowel, an increase of which suggests less response to medical therapy, often necessitating surgery. Overall, bowel US is an excellent, safe, and repeatable choice for routine surveillance and for urgent imaging. We describe an approach to evaluating inflammatory bowel disease and review its features on standard grayscale US with Doppler imaging and show how contrast‐enhanced US and shear wave elastography can distinguish between inflammatory and fibrostenotic bowel.
Kinetic and thermochemical characteristics of the dissociation of Mo(CO)6 and W(CO)6
Authors: Smirnov Vladimir N. , Vlasov Pavel A.
Published: January 2019

The thermal dissociation of gaseous Mo(CO)6 and W(CO)6 in an argon carrier gas, Mo(CO)6 → Mo(CO)5 + CO (1) and W(CO)6 → W(CO)5 + CO (2), is studied over temperature ranges of ∼585–685 K for (1) and ∼690−810 K for (2) at a total gas concentrations of 4 × 10−6 and 4 × 10−5 mol/cm3 by using the shock tube technique in conjunction with absorption spectrophotometry. The measured rate constants are extrapolated to the high‐pressure limit by means of a newly developed procedure, with the resultant expressions for the indicated temperature ranges reading as kd1,∞(T),[s−1] = 1016.12 ± 0.68exp[(−148.8 ± 8.1 kJ/mol)/RT] and kd2,∞(T),[s−1] = 1015.93 ± 0.63exp[(−171.7 ± 8.9 kJ/mol)/RT]. Comparison of the high‐pressure dissociation rate constants with the published data revealed a considerable discrepancy, a tentative explanation of which is given. Based on the obtained high‐pressure dissociation rate constants and the available data on the high‐pressure room‐temperature rate constants for the reverse reaction of recombination, the first bond dissociation energies for these molecules are evaluated and compared with previous determinations, both theoretical and experimental. The enthalpies of formation of Mo(CO)5 and W(CO)5 are determined: ΔfH°(Mo(CO)5, g,  298.15 K) = −644.1  ±  5.6 kJ/mol and ΔfH°(W(CO)5, g,  298.15 K) = −581.9  ±  6.6 kJ/mol. Based on the enthalpies of formation of Mo(CO)5, W(CO)5, Mo(CO)6, and W(CO)6, and the published molecular parameters of these four species, their thermochemical functions are calculated and presented in the form of NASA seven‐term polynomials.
Mandibular muscle attachments in genial advancement surgery for obstructive sleep apnea
Authors: Kim Cherine H. , Loree Nichole , Han Peter S. , Ostby Erin T. , Kwon Daniel I. , Inman Jared C.
Published: January 2019

Objectives/Hypothesis

Genioglossus advancement is performed in select patients with obstructive sleep apnea. Surgical techniques attempt to capture the genial tubercle of the mandible; however, measurements of the genioglossus, geniohyoid, and digastric muscles are poorly delineated. This investigation is the largest anatomic study exploring the muscles of genial advancement surgery and the first to quantitatively characterize muscular attachments relative to the tubercle, providing new insights from an anatomic perspective on optimizing muscular advancement.

Study Design

Cadaveric study.

Methods

Fifty‐three fresh cadaveric mandibles underwent dissection of the genial tubercle and genioglossus, geniohyoid, and digastric muscles.

Results

Genial tubercle, geniohyoid, and genioglossus mean height was 7.78 mm, 5.15 mm, and 6.11 mm, respectively. On average, the geniohyoid began 4.88 mm and ended 10.03 mm from the inferior border of the mandible; the genioglossus 11.91 mm and 18.01 mm, similarly. Intermuscular distance, if present, was 2.67 mm; the muscles overlapped in 28% of cadavers. The combined vertical height of the muscles at their mandibular attachment was 13.94 mm, significantly differing from the height of the genial tubercle. The left and right lateral insertion of the digastric muscles was 19.34 mm and 19.31 mm, respectively, from midline.

Conclusions

The variable range of muscle attachments suggests that genioglossal and geniohyoid attachments extend beyond the genial tubercle and may not originate concentrically from the tubercle, but overlap and lie in very close proximity. Mandibular anterior muscle attachments require anatomic accuracy and an effective operative evaluation of advancement before reproducible, clinically effective osteotomies can be recommended.

Level of Evidence

NA

Laryngoscope, 129:2424–2429, 2019
Effects of the successive planting of Eucalyptus urophylla on soil bacterial and fungal community structure, diversity, microbial biomass, and enzyme activity
Authors: Zhu Lingyue , Wang Xiuhai , Chen Fangfang , Li Chunhua , Wu Lichao
Published: January 2019

Eucalyptus are a widely used short‐rotation species for timber production in South China. There are growing concerns regarding the influences of successive planting of Eucalyptus urophylla on microorganisms and soil. The aim of this work was to determine the effects of the successive planting of E. urophylla on soil characteristics. Five different stands, including 5‐, 10‐, 15‐, and 18‐year‐old E. urophylla plantations (abbreviated as 5yr, 10yr, 15yr, and 18yr, respectively) and one native evergreen broadleaf forest as a 0‐year‐old E. urophylla plantation (abbreviated as CK) were used. All of measured chemical indicators, microbial biomass, and enzyme activities were significantly lower in E. urophylla plantations compared with CK stand. The microbial biomass and enzyme activities significantly decreased in 5yr stand, significantly increased in 10yr stand, and subsequently declined in 15yr and 18yr stands. The relative abundance of Ascomycota in 15yr (77.10%) and 18yr (72.71%) plantations was significantly higher than in other stands. Basidiomycota relative abundance in the E. urophylla plantations was significantly lower than in the CK stand. In addition, the bacterial diversity was significantly decreased in 15yr and 18yr stands, whereas the fungal diversity was the lowest in 5yr stand and significantly increased in 10yr, 15yr, and 18yr stands. Furthermore, structural equation modelling showed that successive planting of E. urophylla decreased the soil bacterial community diversity, microbial biomass, and enzyme activity but increased the fungal community diversity. Thus, successive planting of E. urophylla negatively influenced the soil bacterial diversity, microbial biomass, and enzyme activity and positively influenced soil fungal diversity.
Soil organic matter and texture estimation from visible–near infrared–shortwave infrared spectra in areas of land cover changes using correlated component regression
Authors: Rosero‐Vlasova Olga A. , Vlassova Lidia , Pérez‐Cabello Fernando , Montorio Raquel , Nadal‐Romero Estela
Published: January 2019

Land use changes due to natural and human‐related factors, which include wildfires and crop abandonment, are among the most important drivers of soil degradation and demand regular monitoring. Proximal soil sensing in visible–near infrared–shortwave infrared spectral regions could offer a solution. However, to become operational, optimal combination of data and technique has to be defined. Thus, the purpose of this study was (a) to predict the soil organic matter (SOM) content and soil texture in areas of wildfire burns and crop abandonment in Aragón Province, Northern Spain, from their laboratory reflectance spectra using novel correlated components regression with a step‐down variable selection algorithm (CCR‐SD) and (b) to compare the CCR‐SD and the partial least squares regression (PLSR) methods. The results obtained by the tested methods were similar. CCR‐SD models showed high predictive capacity with coefficients of determination (R2) in the range of 0.80–0.86 and 0.70–0.87 for calibration and validation data sets, respectively, and the highest R2 value was attained in the SOM estimation. Moreover, the CCR‐SD models stand out for the superior accuracy–parsimony relationship: the number of predictors varied from 16 (silt models) to 49 (SOM models). On average, the CCR‐SD calibrations needed less than a half of the predictors employed in PLSR models. This research confirmed that CCR‐SD can be used for monitoring SOM content and texture of soils from visible–near infrared–shortwave infrared spectra in the study area and, probably, in other areas of land use/land cover change and that CCR‐SD can create highly parsimonious models that achieve results comparable with the commonly used PLSR method.
Ultrahigh‐Q Photonic Nanocavity Devices on a Dual Thickness SOI Substrate Operating at Both 1.31‐ and 1.55‐µm Telecommunication Wavelength Bands
Authors: Kuwabara Mitsuki , Noda Susumu , Takahashi Yasushi
Published: January 2019

A feasible method for integrating several silicon (Si) photonic devices with operating wavelengths separated by several hundred nanometers on a single chip will greatly help increasing capacities of small optical communication modules. This work demonstrates the integration of two photonic crystal nanocavity devices that exhibit ultrahigh quality factors (Q) and operate at the 1.31‐ and 1.55‐µm bands. A dual thickness Si‐on‐insulator substrate forms the base of the device. The two nanocavity patterns are defined by electron beam lithography on the thick and thin substrate regions and are transferred to the top Si layer by performing plasma etching only once. All dimensions of the fabricated 1.31‐µm nanocavity are ≈15.5% smaller (1–1.31/1.55) than those of the 1.55‐µm nanocavity; that is, they can be treated with the same photonic band diagram. Both nanocavities exhibit an ultrahigh Q > 2.0 × 106 and enable fabrication of nanocavity‐based Raman lasers for the 1.31/1.55‐µm bands with sub‐microwatt threshold.
Reconfigurable Near‐field Enhancement with Hybrid Metal‐Dielectric Oligomers
Authors: Sun Yali , Sinev Ivan , Zalogina Anastasia , Ageev Eduard , Shamkhi Hadi , Komissarenko Filipp , Morozov Ivan , Lepeshov Sergey , Milichko Valentin , Makarov Sergey , Mukhin Ivan , Zuev Dmitry
Published: January 2019

Tailoring of the near‐field properties of the nanostructures is a significant task for the control of radiation of nanoscale light sources as well as for sensing applications. Generally, this task is solved in plasmonic oligomers on the fabrication step by the choice of geometry or by controlling the excitation light during the experiments. Here, the pronounced modification of the near‐field pattern in hybrid gold‐silicon oligomers by femtosecond laser reshaping by visualizing it with aperture‐type near‐field optical microscope is demonstrated. This effect correlates with a moderate red‐shift of the broadband magnetic dipole resonance of the structure that occurs upon reshaping the gold component of the oligomers. The proposed all‐optical near‐field reconfiguration approach makes hybrid oligomers a promising platform for on‐demand engineering of local field enhancement in metadevices for data recording and sensing.
Chain End‐Functionalized Polymer Brushes with Switchable Fluorescence Response
Authors: Tas Sinem , Kopec´ Maciej , van der Pol Rianne , Cirelli Marco , de Vries Ilse , Bölükbas Deniz A. , Tempelman Kristianne , Benes Nieck E. , Hempenius Mark A. , Vancso G. Julius , de Beer Sissi
Published: January 2019

Herein is described the switchable fluorescence response of poly(methyl methacrylate) (PMMA) brushes. Chain end fluorescein labeled PMMA brushes are prepared by combining surface‐initiated atom transfer radical polymerization (SI‐ATRP) with a copper‐catalyzed alkyne‐azide cycloaddition (CuAAC) click reaction. Successful attachment of fluorescein is confirmed by measuring fluorescence of the as‐prepared films. Utilizing co‐solvency of PMMA in isopropanol‐water mixtures, responsive behavior of the end‐functionalized brushes is demonstrated by measuring the changes in fluorescence intensity between the swollen and collapsed states.
Exosomal protein CD82 as a diagnostic biomarker for precision medicine for breast cancer
Authors: Wang Xiaodan , Zhong Weiliang , Bu Jingya , Li Yuzhong , Li Ruihua , Nie Rong , Xiao Chenyang , Ma Keli , Huang Xiaohua , Li Ying
Published: January 2019

CD82, a member of the tetraspanin superfamily, has been proposed to exert its activity via tetra‐transmembrane protein enriched microdomains (TEMs) in exosomes. The present study aimed to explore the potential of the exosome protein CD82 in diagnosing breast cancers of all stages and various histological subtypes in patients. The results strongly suggest that CD82 expression in breast cancer tissue was significantly lower than that in healthy and benign breast disease tissues. There was a significant negative correlation between CD82 expression in tissues and CD82 content in exosomes, which indicated that CD82 expression was redistributed from tissues to the blood with the development and metastasis of breast cancer.
A note on temporal regularity of second order difference equations
Authors: Dantas Filipe
Published: January 2019

This work deals with the study of maximal ℓp‐regularity of a pair (A,B) of bounded linear operators on a complex Banach space
associated to the second order difference equation un + 2 = Bun + 1 + Aun + fn, where f is a given sequence on
. We obtain results of characterization based on spectral analysis of the discrete sine family, which is the resolvent family of this equation.
Design of an UWB antenna with two slits for 5G/WLAN‐notched bands
Authors: Bong Han‐Ul , Jeong Minjoo , Hussain Niamat , Rhee Seung‐Yeop , Gil Sang‐Keun , Kim Nam
Published: January 2019

In this article, we propose a dual notched‐band antenna with 2 slits for ultra‐wideband (UWB) applications. The antenna consists of a circular ground plane and a patch radiator with having 2 slits and a folding arm. The patch with folding arm is used to achieve UWB band while a V‐shaped and a split ring‐shaped slit are used to eliminate the interference from WLAN and 5G band, respectively. The width and length of the slits are optimized to obtain the necessary band notch characteristics. The prototype of the antenna having a total size of 75 × 10 mm2 is fabricated. Simulated and measured results show that the antenna covers the entire UWB frequency ranging from 2.754 to 14.656 GHz (127%) for VSWR < 2 except at notched bands. Moreover, the antenna successfully notched the WLAN band (5.15‐5.825 GHz) and 5G band (3.4‐3.7 GHz) besides of providing a stable gain and radiation patterns.
On the possibility of linear polarization in elliptical microstrip patch antenna
Authors: Mishra Suvendu Narayan , Konhar Diptimayee , Mishra Debasis , Mishra Rabindra Kishore
Published: January 2019

This article presents a linearly polarized, coaxial probe‐fed elliptical patch antenna, useful for C‐Band application areas. The suggested patch with an eccentricity of 0.866 is simulated. The prototype is fabricated and subsequent measurements are done. A simple theoretical method is developed to determine resonant frequency, which nearly matches with the simulation and experimental values, by incorporating and equivalently modifying the well‐known formulas of rectangular patch antenna. Some comparisons of experimental results of proposed patch with that of rectangular patch antenna suggest the potentiality of elliptical patch in terms of size, bandwidth, and realized gain at resonant frequency. It can also be suggested, here, that eccentricity and feed position determine the nature of polarization.
Bone retouchers from the Middle Palaeolithic site of El Salt, Stratigraphic Unit Xa (Alicante, Spain): First data and comparison with the Middle to Upper Pleistocene European record
Authors: Pérez Leopoldo , Hernández Cristo M. , Galván Bertila
Published: January 2019

Middle Palaeolithic sites frequently present bones with a double function, linked to subsistence and technology, which are generally referred to as “retouchers” or “bone retouchers.” These have been identified in several European sites from the Middle Pleistocene to Holocene, but different explanations of their origin and functionality have been cited. Although bone retouchers were made using various animal parts, they were usually produced from diaphyseal fragments of medium to large hoofed mammals. We present a small assemblage of six bone retouchers recovered from Stratigraphic Unit Xa (52.3 ± 4.6 ka), in the Middle Palaeolithic site of El Salt (Alicante, Spain), and compare our data with previous studies from several sites in south‐western France, northern Italy, and north‐eastern Spain. These tools were generated using diaphyseal fragments from red deer, horses, and other large mammals previously exploited by humans for meat and marrow. Our findings add to the existing knowledge on the behaviour and faunal resource management of the last Neanderthal groups on the western Iberian Peninsula before they disappeared from the region around 45–40 ka.
Association Between Cardiorespiratory Fitness and Risk of Type 2 Diabetes: A Meta‐Analysis
Authors: Qiu Shanhu , Cai Xue , Yang Bingquan , Du Ziwei , Cai Min , Sun Zilin , Zügel Martina , Michael Steinacker Jürgen , Schumann Uwe
Published: January 2019

Objective

This meta‐analysis aimed to (1) quantify the association of cardiorespiratory fitness (CRF) with type 2 diabetes risk in the general population and statin users and (2) investigate the joint effects of CRF and fatness with type 2 diabetes risk.

Methods

Databases were searched for cohort studies reporting the association between CRF and type 2 diabetes risk. Summary hazard ratios (HRs) were obtained using random‐effects models.

Results

Fifteen studies were included. The HRs of type 2 diabetes for every 1–metabolic equivalent increase in CRF were 0.90 (95% CI: 0.86‐0.94) for the general population and 0.92 (95% CI: 0.87‐0.97) for statin users, and the HRs were linearly shaped (both Pnonlinearity > 0.40). Compared with the nonstatin cohort, there was an increased risk of type 2 diabetes in statin users with the lowest and moderate CRF categories, but this was not present in the highest CRF category. The HR of type 2 diabetes for overweight/obesity‐fit category versus normal weight–fit category was larger than that of the normal weight–unfit category versus the normal weight–fit category (Pinteraction = 0.004).

Conclusions

There was an inverse and dose‐dependent association between CRF and type 2 diabetes risk. High CRF may eliminate the diabetogenic effect from statins, yet decreased body weight index seems superior in preventing type 2 diabetes.
A mild and efficient procedure for alkenols oxyselenocyclization by using ionic liquids
Authors: Kostić Marina , Verdía Pedro , Fernández‐Stefanuto Verónica , Puchta Ralph , Tojo Emilia
Published: January 2019

A mild and efficient procedure for the oxyselenocyclization of unsaturated alcohols by treatment with phenylselenyl chloride using ionic liquids as solvents/catalyzers has been developed. The reaction proceeds instantaneously under mild conditions with absolute regioselectivity, using primary, secondary, tertiary, and aromatic alcohols, as well as monosubstituted, disubstituted, and trisubstituted alkenols. This procedure provides a new method for the synthesis of substituted tetrahydrofurans and tetrahydropyrans ethers, the precursors of many biologically active metabolites, avoiding the use of toxic and corrosive catalysts. There are no previous reports of selenium‐mediated cyclofuncionalization reactions in ionic liquids. Taking into the account the good results obtained with [MMIM][MSO4], its ease preparation, low viscosity, low price, and its capacity to be recovered and reused, it was selected as the solvent/catalyzer. Quantum‐chemical calculations (MP2(fc)/6‐311 + G**//B3LYP/6‐311 + G**) has shown that the intramolecular cyclization is promoted by the hydrogen bond formed between the ionic liquid anion and the hydroxyl group of the alkenol.
Triarylpyridinium salts: Synthesis and electrochemical properties
Authors: Dolganov Alexandr V. , Tanaseichuk Boris S. , Pryanichnikova Margarita K. , Ivleva Alina Y. , Chernyaeva Oksana Y. , Grigoryan Karina A. , Chugunova Ekaterina A. , Yurova Veronika Y.
Published: January 2019

The electrochemical properties of the triarylpyridinium salts were studied. The effect of functional substituents on redox properties has been investigated in detail. Electrochemical reduction of salts to the anion in acetonitrile is the result of two one‐electron‐transfer steps through the stage of the radical formation and its subsequent reduction (EE electrochemical mechanism). A correlation between the reduction potentials and the structure of the salts was established.
Growth of Gold Nanoparticles in a Glass Matrix by Continuous Laser Irradiation for Efficient Surface Enhanced Raman Scattering
Authors: Faraj Rim , Goutaland François , Ollier Nadège , Cattaruzza Elti , Vocanson Francis
Published: January 2019

The synthesis of a soda‐lime glass doped by gold nanoparticles (Nps) is achieved using successively thermal poling and continuous wave (cw) ultraviolet (UV) laser exposure. The formation of gold Nps is undoubtedly proved by an absorption band characteristic of their surface plasmon resonance (SPR), and by scanning electron microscopy, which reveals Nps of about 40 nm in diameter, located in the very near surface region of the glass. Absorption spectroscopy also suggests the formation of bimetallic silver‐gold Nps in systems prepared by using thermal poling and laser exposure of a glass previously doped by silver ions using ion exchange. Finally, the low detection limit of Rhodamine 6G (R6G) measured by surface‐enhanced Raman spectroscopy proves the potential of our gold‐doped glass as an efficient Raman substrate, which offers an alternative to silver Nps doped glass.
Assembling of Topological Defects at Neck‐Shaped Membrane Parts
Authors: Kurioz Pavlo , Mesarec Luka , Iglič Aleš , Kralj Samo
Published: January 2019

The impact of intrinsic and extrinsic curvature on the distribution of topological defects (TDs) in neck‐like regions of biological membranes is studied quantitatively. Biological membranes are modeled effectively at the mesoscopic level as two‐dimensional films described in terms of the tensor nematic order parameter field and curvature fields. It is demonstrated that antidefects robustly form at the neck area and can promote a membrane fission. The assembling of antidefects near the catenoid's equatorial ring, where catenoids roughly mimic neck shapes are analyzed in more detail. It is demonstrated that for sufficiently strong curvatures, the effective topological charge Δmeff within a strongly curved region equals zero, and the resulting structures are topologically neutral. Consequently, the total charge of antidefects within the region equals Δm = −ΔmV − ΔmK. In most cases, the positions of antidefects are strongly influenced by the extrinsic curvature.
Tuning Bandgap of Mixed‐Halide Perovskite for Improved Photovoltaic Performance Under Monochromatic‐Light Illumination
Authors: Zhang Xu , Liu Jiang , Song Zhen , Zuo Wentao , Fan Zhengfang , He Xulin , Luo Kun , Ye Qinyan , Liao Cheng
Published: January 2019

Organic–inorganic halide perovskites have emerged as promising materials for optoelectronic devices. This paper focuses on a new application field for perovskite materials as monochromatic‐light conversion devices. First the optical properties of organic–inorganic perovskite semiconductors with bandgaps varying from near‐infrared to visible at room temperature are presented. Two types of hybrid organic–inorganic mixed‐halide perovskites, (FAPbI3)x(MAPbBr3)1‐x and FA0.85MA0.15Pb(IxBr1‐x)3, are adopted for bandgap tuning, an approximate linear variation of bandgaps with the x value is obtained. The relationship between thin film composition and device performance are investigated. Based on the results of the above bandgap tuning, two kinds of devices with bandgap near the wavelength of 683 nm are characterized under monochromatic‐light illumination. A conversion efficiency of up to 40% under 60 mW cm−2 monochromatic‐light illumination is achieved. The results confirm that the perovskite films exhibit sharp optical absorption edge, enabling highly efficient monochromatic‐light conversion device.
Van der Waals effects on structure and optical properties in organic photovoltaics
Authors: Götz Andreas W. , Rodríguez Juan I. , Castillo‐Alvarado Fray L. , Trujillo‐González Daniel E.
Published: January 2019

We have recently reported that dispersion forces can have drastic effects on the structure and charge separation in organic photovoltaics (OPVs) (Martinez et al., J. Phys. Chem. C 121, 20 134 [2017]). Here we investigate dimer complexes formed by the polymer P3HT and the fullerene derivative PCBM. We show how van der Waals (vdW) interactions affect the geometrical structure, which has strong effects on the electronic structure and UV‐Vis absorption spectrum. Time‐dependent density functional theory calculations demonstrate that the experimentally observed blue‐shift of the absorption maximum of P3HT/PCBM OPV cells with respect to pure P3HT results mainly from distortions in P3HT due to vdW interactions between donor and acceptor fragments. Reduced absorption in the red region of the UV‐Vis spectrum results from distortions of P3HT and small charge transfer between P3HT and PCBM. These results are in qualitative agreement with experiments and recent theoretical results on the corresponding solid‐state films.
Laser ablation synthesis of carbon–phosphides from graphene/nanodiamond–phosphorus composite precursors: Laser desorption ionisation time‐of‐flight mass spectrometry
Authors: Mandal Govinda , Vaňhara Petr , Havel Josef
Published: January 2019

Rationale

Carbon–phosphides are new and promising strategic materials with applications e.g. in optoelectronics. However, their chemistry and methods of synthesis are not completely understood, and only a limited number of C–P clusters have been detected up to now. Laser ablation synthesis (LAS) or laser desorption ionisation (LDI) has great potential to generate CmPn clusters in the gas phase and to act as the basis for the development of new technology.

Methods

The LAS of carbon phosphides using mixtures of nano‐carbon sources (graphene, nanodiamonds) with phosphorus allotropes (red, black, and phosphorene) was examined. Since phosphorene is not commercially available, it was synthesised. A reflectron time‐of‐flight mass spectrometer was used to produce and identify the C–P clusters. A transmission electron microscope was used to characterise the prepared composites.

Results

LDI of various carbon–phosphorus composites generated a range of carbon–phosphides. From graphene–red phosphorus, CmP+ (m = 3–47), CmP2+ (m = 2–44), CmP3+ (m = 1–42), CmP4+ (m = 1–39), CmP5+ (m = 1–37), CmP6+ (m = 1–34), CmP7+ (m = 1–31), CmP8+ (m = 1–29), CmP9+ (m = 1–26), CmP10+ (m = 1–24), CmP11+ (m = 1–21), and CmP12+ (m = 1–19) clusters were detected, while nanodiamond composites with red/black phosphorus and with phosphorene yielded C24P5 + 2n+ (n = 0–28), C24P5 + 2n+ (n = 0–16), and C24P5 + 2n+ (n = 0–14) clusters, respectively. In total, over 300 new carbon–phosphide clusters were generated.

Conclusions

The novel series of carbon–phosphide clusters generated from graphene or nanodiamond composites with red/black phosphorus or with phosphorene demonstrated rich carbon–phosphide chemistry that might inspire the development of novel nano‐materials with specific properties.
Does women's political empowerment matter for improving the environment? A heterogeneous dynamic panel analysis
Authors: Lv Zhike , Deng Chao
Published: January 2019

According to the UN Agenda 21 in 1992, women were regarded as a very important part in achieving sustainable development. In this agenda, participation, equality, and empowerment for females were emphasized as bases for sustainable development. In this paper, we make an attempt to explore the relationship between women's political empowerment (WPE) and CO2 emissions. To that end, we apply panel‐cointegration techniques to investigate both long‐term and short‐term effects of WPE on the environment in 72 countries during 1971–2012. The results from the pooled mean group (PMG) estimator indicate that, in the long run, CO2 emissions decrease by about 11.51 percent points in response to a one‐unit increase in the index of WPE after controlling for a variety of other factors. However, the short‐term estimated coefficient of WPE is statistically insignificant. Moreover, further study shows that women's civil society participation has the largest effect, followed by political participation. Another noteworthy result is the effect of energy intensity. We find that both the long‐term and short‐term estimated coefficient of energy intensity are positive and highly statistically significant, but the magnitude of the short‐term estimated coefficient is lower than the long‐term one. This comparison suggests that the influence of energy intensity on CO2 emissions would usually take some time to materialize fully. From a policy perspective, our estimation results suggest that improving the status of women worldwide, especially in the developing countries, can reduce CO2 emissions.
Organoacid‐Decorated NiFe2O4 Nanoparticles: An Efficient Catalyst for Green Synthesis of 2H‐Indazolo[2, 1‐b]phthalazine‐Triones and Pyrimido[1,2‐a]benzimidazoles
Authors: Hamidinasab Mahdia , Mobinikhaledi Akbar
Published: January 2019

Organo‐Sulfonic acid tags anchored on magnetic titana coated NiFe2O4 nanoparticles (nano‐NiFe2O4@TiO2‐SiO2‐Pr‐DEA‐OSO3H) was prepared and characterized by various analysis methods including Fourier transform infrared (FT‐IR) spectroscopy, field emission scanning electron microscopy (FE‐SEM), energy dispersive X‐ray spectroscopy (EDS), vibrating sample magnetometer (VSM), X‐ray diffraction (XRD) and thermo gravimetric analysis (TGA). These modified nanoparticles were used as efficient and recoverable hybrid nanocatalyst in multicomponent synthesis of some phthalazine‐trione and benzo[4,5]imidazo[1,2‐a]pyrimidine derivatives under green conditions. High yields within shorter reaction times, simple purification, and environmentally mild reaction conditions are some advantages of this protocol.
Fluorescent Gadolinium(III)‐Oligopeptide Complexes and Carbon Nanotube Composite as Dual Modality Anticancer Agents
Authors: Sheikh Aasif Hassan , Khalid Anam , Khan Farah , Begum Ameerunisha
Published: January 2019

In search of non‐platinum based anticancer drugs, we have synthesized and characterized a new class of three gadolinium(III)‐oligopeptides [Gd(L1)2(NO3)2][NO3] (1, L1=l‐aspartyl(OMe)‐N‐boc‐l‐aspartyl‐l‐aspartyl (OMe)), [Gd(L2)2(NO3)2][NO3] (2, L2=N‐fmoc‐l‐arginyl‐(Pbf)‐glycyl‐l‐aspartyl(OMe)), [Gd(L3)(NO3)3] (3, L3=N‐fmoc‐l‐arginyl‐(Pbf)‐l‐arginyl(OMe) and a carbon nanotube composite, 1@CNT 4. The three oligopeptides, L1 – L3 were prepared in a novel synthetic route using tetramethyl benzotriazolyl uronium hexaflurophosphate (HBTU) as a peptide coupling reagent. Confocal microscopic analysis of the gadolinium(III)‐oligopeptides, 1, 2 and CNT composite, 1@CNT 4 indicate that they display white and green light emissions upon excitations at λ, 405 and 488 nm with characteristic patterns. The oligopeptides, L1 & L3 display in vitro anticancer activity on HeLa cells with IC50 values in one mM concentration whereas the IC50 of RGD‐based oligopeptide was found to be 1 μM. The IC50 of gadolinium(III)‐oligopeptide, 1 and the CNT composite, 4 were found to be 1 μM and 10 nM. The transmission electron microscopic investigation of the HeLa cells treated with the composite 4 confirm the cellular uptake and indicate the presence of CNTs in the cytoplasm and that CNTs appear like bullets carrying the gadolinium(III)‐triaspartate, 1.
Syntheses, X‐Ray Crystal Structures, Emission Properties and DFT Calculations of Monoprotonated Polypyridines
Authors: Yoshikawa Naokazu , Yamazaki Shoko , Kato Natsumi , Kubota Akari , Sawai Mika , Noda Kaoru , Kanehisa Nobuko , Inoue Tsuyoshi , Nakata Eiji , Takashima Hiroshi
Published: January 2019

Monoprotonated compounds [(L)HPF6] were prepared by the reaction of (L=bpy, phen, dpphen, bqn and ppy) with concentrated HCl in water. Monoprotonated pyridine rings are hydrogen bonded intramolecularly to the adjacent pyridine ring and intermolecularly to the adjacent PF6− in compounds. These hydrogen bonds restrain the nonradiative decay to produce intense emission. Density functional theory was applied to interpret the planarity in compounds. The attachment of one proton to the nitrogen in [(dpphen)HPF6] and [(bqn)HPF6] leads to the strong emission in acetonitrile (Φ = 0.046 and 0.097, respectively). In particular, the attachment of one proton to the ppy nitrogen results in exhibiting a strong emission with a large quantum yield (Φ = 0.264).
Facile Non‐Transition Metal‐Catalyzed Synthesis of 2‐Thioxo‐2,3‐dihydroquinazolin‐4(1H)‐one Derivatives via One‐Pot Multicomponent Reactions
Authors: Bahadorikhalili Saeed , Rahimzadeh Golnaz , Kianmehr Ebrahim , Ansari Samira , Hamedifar Haleh , Mahdavi Mohammad
Published: January 2019

In this paper, a novel method is introduced for the synthesis of 3‐substituted 2‐thioxo‐2,3‐dihydroquinazolin‐4(1H)‐one derivatives. This methodology is based on the multicomponent one‐pot reaction of isatoic anhydride, amines, chloroform and sulfur in basic conditions. The products are obtained in highest efficiency when the reaction is performed in 1,4‐dioxane as the solvent in the presence of potassium tert‐butoxide as the base. The reaction showes to be efficient and simple for the preparation of these compounds. In addition, this method is general and different aromatic or aliphatic amines are used and the desired products are isolated in high yields. A possible mechanism for the reaction is proposed, which consisted the dichlorocarbene formation under the basic conditions.
Selection of Graphite Pencil Grades for the Design of Suitable Electrodes for Stacking Multiple Single‐Inlet Paper‐Pencil Fuel Cells
Authors: Arun Ravi Kumar , Gupta Vinay , Singh Preeti , Biswas Gautam , Chanda Nripen
Published: January 2019

We present a single‐inlet paper‐pencil based microfluidic fuel cell which works on the capillary driven fluid flow of a mixture of fuel (formic acid) and electrolyte (dilute sulfuric acid) solutions as a single entity. Different types of pencils are used to prepare the graphite electrodes to observe their effect on the fuel cell performance. The graphite electrodes are porous and act as a gas diffusion electrode which breaths in oxygen directly from the quiescent air and out CO2 from the cell. The paper fuel cell also fabricated in different dimensions and connected as cell‐stacks to enhance its performance. The paper‐pencil device generates maximum open circuit potential of ∼2.5 V in series combination and maximum current density of ∼ 82 mA cm−2 and power density of ∼ 100 mW cm−2 in parallel combination. Later, rGO−Cu/CuO nanocomposite embedded electrodes are used to observe their effect on the device performance.
Synthesis, In Vitro Anti‐Inflammatory Activity and Molecular Docking of Butyrate Benzophenone Compound
Authors: Li Yunlan , Yang Lu , Chen Xi , Niu Siqing , Ban Shurong , Feng Xiue , Li Qingshan
Published: January 2019

Twelve new butyric acid ester‐containing benzophenone compounds were synthesized by Friedel‐Crafts acylation reaction, Esterification reaction and Clemmensen reduction reaction. Biological evaluation indicated that all compounds exhibit certain anti‐inflammatory activities against Lipopolysaccharides (LPS) induced inflammatory in mouse macrophages (RAW264.7). In particular, a novel compound,4‐[3‐ isobutyl‐4‐methoxy‐5 ‐(pyrrolidine‐1‐carbonyl)‐phenyl]‐butyric acid ethyl ester (7 g) showed the highest anti‐inflammatory activity with the IC50 value of 18.60 ± 7.79 μM for nitric oxide (NO) which is better than that of the positive control Ibuprofen (IC50=37.6±6.9 μM ) and the positive control compound of COX‐2 inhibitor (IC50=47.2±0.4 μM ), indicating that it could be a potential candidate for further development as a anti‐inflammatory drug.
Reformatsky Reagent Promoted Acetylation of Primary and Secondary Aliphatic Alcohols Using Ethyl Acetate as an Acetyl Donor
Authors: Fujihara Rina , Nakata Kenya
Published: January 2019

The reaction system of a Reformatsky reagent as a promoter and EtOAc as a solvent and acetyl donor was found to achieve efficient acetylation of a variety of primary and secondary aliphatic alcohols under mild conditions. The reaction can be carried out by a simple one‐pot operation and does not require heating. The reaction shows a high tolerance for various functional groups and chemoselectivity, such that the phenolic hydroxyl groups do not react. Furthermore, the reaction can be used for gram‐scale acetylation.
Enhanced Solar Conversion of CO2 to CO Using Mn‐doped TiO2 Based on Photo‐thermochemical Cycle
Authors: Deng Bowen , Xu Chenyu , Li Zheng , Huang Wenhui , Wu Qiliang , Zhang Yanwei , Ni Mingjiang , Cen Kefa
Published: January 2019

Photo‐thermochemical cycle (PTC) is a promising method to converting CO2 to solar fuels. To study the mechanism of CO2 reduction based on PTC, sol‐gel synthesized titanium dioxide (ST) and Mn‐doped TiO2 (MT) films were produced and applied to the PTC under simulated solar light irradiation. Commercial P25 (PT) was used as a reference. Experiments show that Mn‐doped TiO2 produced more CO than undoped TiO2 and P25. The average CO production of 1.0 wt% MT by the PTC was 32.19 μmol⋅m−2⋅h−1), 4.36 times than that of ST and 3.63 times that of PT. Various characterization methods were conducted to investigated the effect of Mn ions doping on the photoresponse and charge transfer of samples. Density functional theory (DFT) calculations were also performed to verify the analysis and enhance the PTC mechanism. In conclusion, several key factors that Mn ions promote CO2 conversion have been clarified.