bluuebunny/crossref_metadata_2025 huggingface dataset:
Diagnostic and Treatment Standards in Idiopathic Pulmonary Fibrosis in the Era of Antifibrotic Drugs in Poland: A Real-World Practice Survey
Authors: Majewski Sebastian , Lewandowska Katarzyna , Martusewicz-Boros Magdalena , Piotrowski Wojciech
Published: January 2020

Introduction: Currently, only two drugs have been shown to modify the inevitable natural history of idiopathic pulmonary fibrosis (IPF). Changes in the reimbursement policy for antifibrotic drugs in Poland have led to the availability of pirfenidone from January 2017 and nintedanib from March 2018 for the treatment of Polish patients with IPF. This study aimed to evaluate the possible changes and shortcomings in the clinical practice standards in IPF in the era of access to antifibrotic therapy in Poland. Material and methods: A real-world data survey was performed among physicians attending the Polish Respiratory Society Congress held in May 2018. The present survey was a follow-up to the previous survey undertaken in 2016, before the availability of antifibrotics in Poland. Results: A total of 99 physicians participated in the survey, among which 80% were pulmonologists. The majority of participants (83%) represented hospital-based clinicians and most of them (93%) were involved in interstitial lung diseases (ILD) management. As many as 63% of the respondents elaborate the final diagnosis of IPF working with the expert radiologist routinely, 47% do that in the cooperation with other pulmonologists, and if a biopsy was performed 39% discuss its results with the expert pathologist. Bronchoalveolar lavage (BAL) and surgical lung biopsy (SLB) would never be recommended in the differential diagnosis of IPF by 9% and 16% of the respondents, respectively. Corticosteroids (CS) or a combination of CS and immunosuppressants (IS) is still recommended by 22% of participants. Proton pump inhibitors (PPI) in the case of symptomatic GERD are prescribed by 44% of the respondents, and 12% prescribe PPI regardless of GERD symptoms. Pirfenidone is used by 70%, and nintedanib by 48% of the respondents. Only 39% of the respondents refer patients with IPF to professional rehabilitation centers. Conclusions: The level of cooperation between pulmonologists and other specialists in the diagnostic workup of IPF is unsatisfactory. IPF treatment practices in the era of access to effective drugs in Poland require immediate improvement. There is an urgent need to develop the local Polish practical Guideliness to improve the management of IPF.
Exogenous Lipoid Pneumonia Induced by Nasal Instillation of Paraffin Oil
Authors: Bartosiewicz Małgorzata , Zimna Katarzyna , Lewandowska Katarzyna , Sobiecka Małgorzata , Dybowska Małgorzata , Radwan-Rohrenschef Piotr , Szturmowicz Monika , Tomkowski Witold
Published: January 2020

Lipoid pneumonia is a rare pulmonary disease, classified in terms of the source of lipid exposure into two variants: exogenous and endogenous. We present a patient with exogenous lipoid pneumonia, acquired after chronic exposure to paraffin oil-containing nasal drops. The diagnosis was established by demonstration of lipid-laden macrophages in bronchoalveolar lavage, chest computed tomography results and a history of lipid exposure.
Tales of Hope, Tastes of Bitterness
Authors: Driessen Miriam
Published: January 2020

Tales of Hope and Tastes of Bitterness sheds light on Chinese-led development from below, revealing its contested nature. Zooming in on everyday encounters between Chinese managers and Ethiopian laborers on a road construction site in Tigray, northern Ethiopia, the book shows that Ethiopians define Chinese-led development as much as they are defined by it. By mobilizing civic and legal authorities, Ethiopian workers have managed to increase their leverage to such a degree that they occasionally outplay Chinese management. On the other hand, Chinese narratives of bitterness reveal that Chinese road builders perceive themselves as lacking agency. Speaking, as they do, of thwarted goodwill, these narratives are not only linked to the everyday challenges of Chinese–Ethiopian encounters and the chasm between their confident expectations and the much less rosy realities on the ground, but also to workers’ socioeconomic backgrounds and their state of suspension, as they try to stay afloat in the competitive Chinese society to which they hope one day to return.
Diagnostic Value of Endobronchial Ultrasonography with A Guide Sheath Combined with Virtual Bronchoscopic Biopsy for Pulmonary Peripheral Lesions
Authors: Zhang Huanan , Wang Chaochao , Zhang Yuan , Xu Shaohua , Wang Ying , Wang Wei
Published: January 2020

Background: Lung cancer is not only the most common tumor, but also the tumor of supreme incidence and death rate in all malignant tumors. Bronchoscopy has been widely used in the diagnosis of space occupying lung lesions, but the diagnostic rate of pulmonary peripheral lesions (PPL) is relatively low. The emergence of intra-airway ultrasound technology is a milestone for the development of respiratory endoscopy technology. The appearance of miniature lung ultrasound probe has greatly improved the accuracy of diagnosis of peripheral lung diseases, especially peripheral lung cancer. In recent years, guided sheath (GS) endobronchial ultrasonography with trans-bronchial lung biopsy (EBUS-TBLB) has been used to diagnose pulmonary peripheral lesions. The diagnostic rate is over 70%, and the incidence of adverse reactions is low. Objectives: The aim of the current study was to determine the diagnostic value of endobronchial ultrasonography with a guide sheath combined with virtual bronchoscopic biopsy (EBUS-GS-TBLB+VB) for PPL, and to find the factors that were correlated with greater diagnostic accuracy of EBUS-GS-TBLB. Patients and Methods: In this retrospective study, 87 patients with PPL were grouped according to different instrument-guided TBLB techniques, which included conventional TBLB, EBUS-GS-TBLB (E-TBLB), and EBUS-GS-TBLB+VB (E+V-TBLB). The diagnostic accuracy and duration of the operations were compared. Correlative factors were determined and any complications related to the operations were recorded. Results: The diagnostic accuracy of E+V-TBLB (16/20, 80%) and E-TBLB (22/29, 75.9%) were significantly better (P < 0.05) than that of TBLB (18/38, 47.4%), and the duration of the operation (minutes) was significantly shorter in E+V-TBLB (7.78 ± 2.0) than in E-TBLB (12.97 ± 3.4) (P = 0.018). We found that lesions with a diameter ≥ 2 cm (27/29, 93.1%) that were probe-penetrable (30/32, 93.5%), and with a computed tomography (CT) attenuation value > 20 HU were related to higher diagnostic accuracy in EBUS-GS-TBLB. All the patients tolerated the TBLB operations well. Bleeding occurred in one patient from the TBLB group. There was no pneumothorax, hemoptysis, or other complications in the other groups. Conclusion: The diagnostic accuracy of EBUS-GS-TBLB was much greater than that of TBLB, and patients showed better tolerance to it.
Evaluation of Antimicrobial Effect of Ferulago angulata on Staphylococcus aureus Growth Isolated From Subclinical Mastitis, in Vitro Study
Authors: Bohlouli Somayeh , Hasanvand Sara
Published: January 2020

Background: Staphylococcus aureus is one of the important causative agents in mastitis. Objectives: The aim of this study was determination antimicrobial effect of Ferulago angulata and different common therapeutic antibiotics on growth of Staphylococcus aureus isolated from subclinical mastitis cases. Methods: In this study the antibacterial effect of Ferulago angulata essential oil, aqueous and hydro alcoholic extract on Staphylococcus aureus growth was done and compared with common therapeutic antibiotics such as tetracycline, erythromycin, kanamycin and gentamicin by diffusion disk method. Minimum inhibitory concentration and minimum bactericidal concentration were tested through tube standard method. Results: Antimicrobial effect of essential oil and hydro alcoholic extract was increased by dose-dependently. 40 mg/mL extract and 20% essential oil are the highest dose with antimicrobial effect. Extract of Ferulago angulata has maximum antibacterial activity on the growth of S. aureus. Conclusions: Ferulago angulata had remarkable anti-bacterial effect on Staphylococcus aureus growth isolated from subclinical mastitis cases. In comparison Ferulago angulata essential oil was more powerful than extract. Regarding the fact that antibiotic resistance is growing, Ferulago angulata as an herbal plant with anti-bacterial effect could be used in Staphylococcus aureus isolated from subclinical mastitis cases.
Lo performativo en prácticas de arte y diseño actuales vinculadas a procesos de innovación social. El caso de La venezia che non si vede y de La borda
Authors: Costa Gomez Tània
Published: January 2020

En este artículo se propone abordar la capacidad performativa de ciertas prácticas artísticas y de diseño actuales que inciden en contextos sociales con la voluntad de afectar e influir en los estilos de vida y hábitos de lo cotidiano. En el caso del arte podría decirse que son iniciativas que cuentan con antecedentes como la tradición contemporánea de la estética relacional y el arte contextual, mientras que en diseño provienen de una visión avanzada del diseño de sistemas y servicios. En ambos casos, en esta investigación nos interesan los proyectos implicados en procesos de cambio social y que tengan como objetivo procurar vías posibles de transición hacia modos de vida sostenibles. Por lo mismo, se trata de producciones que abarcan la visión social, ética, política y estética.
Estatus y estado del diseño más allá del objeto
Authors: Medina Reinón Pedro
Published: January 2020

.
Mar de Nubes. Cuerpo de Cristal
Authors: González Dionisio
Published: January 2020

.
Stop codon context influences genome-wide stimulation of termination codon readthrough by aminoglycosides
Authors: Wangen Jamie R , Green Rachel
Published: January 2020

Stop codon readthrough (SCR) occurs when the ribosome miscodes at a stop codon. Such readthrough events can be therapeutically desirable when a premature termination codon (PTC) is found in a critical gene. To study SCR in vivo in a genome-wide manner, we treated mammalian cells with aminoglycosides and performed ribosome profiling. We find that in addition to stimulating readthrough of PTCs, aminoglycosides stimulate readthrough of normal termination codons (NTCs) genome-wide. Stop codon identity, the nucleotide following the stop codon, and the surrounding mRNA sequence context all influence the likelihood of SCR. In comparison to NTCs, downstream stop codons in 3′UTRs are recognized less efficiently by ribosomes, suggesting that targeting of critical stop codons for readthrough may be achievable without general disruption of translation termination. Finally, we find that G418-induced miscoding alters gene expression with substantial effects on translation of histone genes, selenoprotein genes, and S-adenosylmethionine decarboxylase (AMD1).
NEK2 induces autophagy‐mediated bortezomib resistance by stabilizing Beclin‐1 in multiple myeloma
Authors: Xia Jiliang , He Yanjuan , Meng Bin , Chen Shilian , Zhang Jingyu , Wu Xuan , Zhu Yinghong , Shen Yi , Feng Xiangling , Guan Yongjun , Kuang Chunmei , Guo Jiaojiao , Lei Qian , Wu Yangbowen , An Gang , Li Guancheng , Qiu Lugui , Zhan Fenghuang , Zhou Wen
Published: January 2020

NEK2 is associated with drug resistance in multiple cancers. Our previous studies indicated that high NEK2 confers inferior survival in multiple myeloma (MM); thus, a better understanding of the mechanisms by which NEK2 induces drug resistance in MM is required. In this study, we discovered that NEK2 enhances MM cell autophagy, and a combination of autophagy inhibitor chloroquine (CQ) and chemotherapeutic bortezomib (BTZ) significantly prevents NEK2‐induced drug resistance in MM cells. Interestingly, NEK2 was found to bind and stabilize Beclin‐1 protein but did not affect its mRNA expression and phosphorylation. Moreover, autophagy enhanced by NEK2 was significantly prevented by knockdown of Beclin‐1 in MM cells, suggesting that Beclin‐1 mediates NEK2‐induced autophagy. Further studies demonstrated that Beclin‐1 ubiquitination is decreased through NEK2 interaction with USP7. Importantly, knockdown of Beclin‐1 sensitized NEK2‐overexpressing MM cells to BTZ in vitro and in vivo. In conclusion, we identify a novel mechanism whereby autophagy is activated by the complex of NEK2/USP7/Beclin‐1 in MM cells. Targeting the autophagy signaling pathway may provide a promising therapeutic strategy to overcome NEK2‐induced drug resistance in MM.
Toc75‐V/OEP80 is processed during translocation into chloroplasts, and the membrane‐embedded form exposes its POTRA domain to the intermembrane space
Authors: Gross Lucia E. , Spies Nicole , Simm Stefan , Schleiff Enrico
Published: January 2020

The insertion of membrane proteins requires proteinaceous complexes in the cytoplasm, the membrane, and the lumen of organelles. Most of the required complexes have been described, while the components for insertion of β‐barrel‐type proteins into the outer membrane of chloroplasts remain unknown. The same holds true for the signals required for the insertion of β‐barrel‐type proteins. At present, only the processing of Toc75‐III, the β‐barrel‐type protein of the central chloroplast translocon with an atypical signal, has been explored in detail. However, it has been debated whether Toc75‐V/ outer envelope protein 80 (OEP80), a second protein of the same family, contains a signal and undergoes processing. To substantiate the hypothesis that Toc75‐V/OEP80 is processed as well, we reinvestigated the processing in a protoplast‐based assay as well as in native membranes. Our results confirm the existence of a cleavable segment. By protease protection and pegylation, we observed intermembrane space localization of the soluble N‐terminal domain. Thus, Toc75‐V contains a cleavable N‐terminal signal and exposes its polypeptide transport‐associated domains to the intermembrane space of plastids, where it likely interacts with its substrates.
Dithieno[3,2‐b:2ʹ,3ʹ‐d]pyrrol‐Fused Asymmetrical Electron Acceptors: A Study into the Effects of Nitrogen‐Functionalization on Reducing Nonradiative Recombination Loss and Dipole Moment on Morphology
Authors: Gao Wei , Liu Tao , Sun Rui , Zhang Guangye , Xiao Yiqun , Ma Ruijie , Zhong Cheng , Lu Xinhui , Min Jie , Yan He , Yang Chuluo
Published: January 2020

Energy loss (Eloss) consisting of radiative recombination loss (ΔE1 and ΔE2) and nonradiative recombination loss (ΔE3) is considered as an important factor for organic solar cells (OSCs). Herein, two N‐functionalized asymmetrical small molecule acceptors (SMAs), namely N7IT and N8IT are designed and synthesized, to explore the effect of N on reducing Eloss with sulfur (S) as a comparison. N7IT‐based OSCs achieve not only a higher PCE (13.8%), but also a much lower Eloss (0.57 eV) than those of the analogue (a‐IT)‐based OSCs (PCE of 11.5% and Eloss of 0.72 eV), which are mainly attributed to N7IT's significantly enhanced charge carrier density (promoting JSC) and largely suppressed nonradiative Eloss by over 0.1 eV (enhancing VOC). In comparison, N8IT, with an extended π‐conjugated length, shows relatively lower photovoltaic performance than N7IT (but higher than a‐IT) due to the less favorable morphology caused by the excessively large dipole moment of the asymmetrical molecule. Finally, this work sheds light on the structure–property relationship of the N‐functionalization, particularly on its effects on reducing the Eloss, which could inspire the community to design and synthesize more N‐functionalized SMAs.
Estimation of the dominant size enlargement mechanism in spray fluidized bed processes
Authors: Rieck Christian , Bück Andreas , Tsotsas Evangelos
Published: January 2020

This work deals with estimating the dominant size enlargement mechanism in spray fluidized beds. A new process model is presented, which consists of population balances and a heat‐ and mass‐transfer model. New methods to incorporate the wet surface fraction and the Stokes criterion are proposed, which allow for the probability of wet collisions and the probability of successful wet collisions to be calculated. The product of these parameters, the probability of successful collisions, is linked to the dominant size enlargement mechanism. Simulation studies were performed to investigate the influence of inlet gas temperature, viscosity, droplet size, and contact angle on the probability of successful collisions. Further simulation results based on experiments available in literature suggest that exceeding a probability of successful collisions of 0.001 is sufficient for agglomeration to become dominant. Otherwise, layering will be the dominant size enlargement mechanism. Finally, regime maps of layering and agglomeration are constructed.
A trust‐region framework for integration of design and control
Authors: Rafiei Mina , Ricardez‐Sandoval Luis A.
Published: January 2020

A trust‐region approach is presented to address the simultaneous design and control of large‐scale systems under uncertainty. The key idea is to represent the system using power series expansions (PSEs) as piecewise models in an iterative manner while the validity of those expansions is certified in a trusted region. The mean of squared errors is used as a metric to quantify the accuracy of the PSE approximations. Identified search regions specify the boundaries of the decision variables for the PSE‐based optimization problems. The proposed algorithm shows a significant accomplishment in locating dynamically feasible and near‐optimal design and operating conditions. The proposed approach was tested in a wastewater treatment plant and the Tennessee Eastman process. The results indicate that the proposed methodology leads to more economically attractive and reliable designs while maintaining the dynamic operability of the system in the presence of disturbances and uncertainty.
Inflammatory and oxidative stress biomarkers induced by silica exposure in crystal craftsmen
Authors: Scalia Carneiro Ana Paula , Algranti Eduardo , Chérot‐Kornobis Nathalie , Silva Bezerra Frank , Tibiriça Bon Ana Maria , Felicidade Tomaz Braz Nayara , Soares Souza Débora Maria , de Paula Costa Guilherme , Bussacos Marco Antônio , de Paula Alves Bezerra Olívia Maria , Talvani André
Published: January 2020

Background

Identification of biomarkers associated with the diagnosis and prognosis of silicosis would be highly advantageous in the clinical setting. The aim of this study is to evaluate inflammatory and oxidative stress biomarkers in subjects exposed to silica.

Methods

A cross‐sectional study of crystal craftsmen currently (n = 34) or formerly (n = 35) exposed and a group of nonexposed subjects (n = 12) was performed. Personal respirable dust samples were collected. Plasma inflammatory mediators (bone morphogenetic protein‐ BMP2 and chemokines CXCL16, and CCL5), oxidative stress enzymes (thiobarbituric acid reactive substances [TBARs] and superoxide dismutase [SOD]), and nitrite (NO2−) were analyzed in parallel with nitric oxide in exhaled breath (FeNO).

Results

Being currently or formerly exposed to silica was related to increased levels of CXCL16 and TBARs. Currently, exposed subjects showed decreased levels of SOD. Thirty‐seven craftsmen with silicosis (26 formerly and 11 currently exposed) showed higher levels of CXCL16, which was positively associated with the radiological severity of silicosis. Compared with the nonexposed, subjects with silicosis had higher levels of TBARs and those with complicated silicosis had lower levels of SOD. In multivariate analysis, higher levels of CXCL16 were associated with exposure status and radiological severity of silicosis. Smoking was not a confounder. FeNO did not distinguish between the exposure status and the presence of silicosis.

Conclusion

CXCL16 emerged as a potential biomarker that could distinguish both silica exposure and silicosis. TBARs were elevated in exposed individuals. However, their clinical applications demand further investigation in follow‐up studies of representative samples.
Full employment history of Danish firefighters potentially involving additional exposures, 1964‐2015
Authors: Elbæk Pedersen Julie , Ugelvig Petersen Kajsa , Hansen Johnni
Published: January 2020

Background

This study aimed to demonstrate the possibility of using data on full employment history to describe occupational patterns of Danish firefighters that may indicate additional hazards encountered by these workers.

Methods

An established cohort of Danish full‐time and part‐time/volunteer firefighters was used in the study (N = 9952) as well as occupational history covering the period 1964‐2015, which was retrieved from a nationwide pension fund with compulsory membership. The most frequently held employments other than firefighting, together with temporal patterns of these employments, were explored in descriptive analyses.

Results

Besides working in the firefighter service, both full‐time and part‐time/volunteer firefighters had frequently been employed in the military and the police (55% and 38%) and more than 10% of both types of firefighters in a number of blue‐collar jobs, including construction‐related jobs (eg, masonry, joining, carpentry, insulation, and installation), laundry and dry cleaning, the auto industry, and rubber and plastic production. Part‐time/volunteer firefighters had more frequently been employed in the machine industry, fabricated metal production, the wood and furniture industry, and farming. Both types of firefighters were initially employed in other jobs before their employment in firefighting.

Conclusion

The cohort of Danish firefighters had frequently been working in other professions potentially exposing them to additional hazardous exposures, and occupational patterns varied by type of firefighter employment. Accounting for full employment history is, for that reason, considered essential when exploring associations between specific professions and health outcomes.
A semi‐quantitative job exposure matrix for dust exposures in Swedish soft tissue paper mills
Authors: Neitzel Richard L. , Andersson Marianne , Lohman Susanna , Sällsten Gerd , Torén Kjell , Andersson Eva
Published: January 2020

Background

Total paper dust exposure has been associated with respiratory problems among workers in the soft tissue paper industry. However, a comprehensive job exposure matrix (JEM) has not been developed for application to this industry. Our study was intended to address this need and to support further studies of mortality and morbidity in a cohort of Swedish workers from this industry.

Methods

We evaluated four participating soft tissue paper mills in Sweden. We combined information on process and equipment status from the mills with knowledge of the mills obtained through research efforts and paper dust measurements made at all four mills to develop a semi‐quantitative JEM with seven dust exposure levels. The JEM was targeted at workers enrolled into a soft tissue paper mill cohort and working any time between 1960 and 2009.

Results

The JEM includes a total of 14 421 cells, with each cell corresponding to the exposure for a job title, department, or work location for a one‐year period. Exposure levels in the JEM were estimated to decline at three of the four mills from 1971 to 2009, but overexposures (ie, exceedances of the relevant occupational exposure limits) remained common at the end of the period.

Conclusions

The JEM results highlight the need for ongoing exposure control efforts in the soft tissue paper industry, and will inform ongoing epidemiological studies of the health effects of exposure to paper dust in Sweden. It is freely available for use by other researchers.
Airway abnormalities in very early treated infantile‐onset Pompe disease: A large‐scale survey by flexible bronchoscopy
Authors: Yang Chia‐Feng , Niu Dau‐Ming , Tai Shyh‐Kuan , Wang Ting‐Hao , Su Hsiao‐Ting , Huang Ling‐Yi , Soong Wen‐Jue
Published: January 2020

Early enzyme replacement therapy (ERT) improve long‐term outcomes in patients with infantile‐onset Pompe disease (IOPD). Our cohort of patients with IOPD at Taipei Veterans General Hospital (TVGH) joined Taiwan Pompe newborn screening program from 2008, testing more than one million newborns until 2018. By 2010, we had established rapid diagnostic strategies. Now, the average age of ERT initiation starts at an average age of <10 days‐old, the earliest group in the world. However, they still presented some airway problems. We present a retrospective study focused on airway abnormalities in these patients along 8 years of observation. Fifteen patients with IOPD, who received very early treatment at a mean age of 8.94 ± 3.75 days, underwent flexible bronchoscopy (FB) for dynamic assessment of the whole airway. Long‐term clinical outcomes and relevant symptoms of the upper airway were assessed. All patients in the study had varying degrees of severity of upper airway abnormalities and speech disorders. The three oldest children (Age 94, 93, and 88 months, respectively) had poor movement of the vocal cords with reduced abduction and adduction and had silent aspiration of saliva through the glottis during respiration. This is the largest cohort study presented to date about airway abnormalities in very early treated patients with IOPD patients by FB. Despite very early treatment, we observed upper airway abnormalities in these IOPD patients. In IOPD, upper airway abnormalities seem inevitable over time. We suggest early and continuous monitoring for all IOPD patients, even with early and regular treatment.
Refining critical regions in 15q24 microdeletion syndrome pertaining to autism
Authors: Liu Yi , Zhang Yanqing , Zarrei Mehdi , Dong Rui , Yang Xiaomeng , Zhao Dongmei , Scherer Stephen W. , Gai Zhongtao
Published: January 2020

Chromosome 15q24 microdeletion syndrome is characterized by developmental delay, facial dysmorphism, hearing loss, hypotonia, recurrent infection, and other congenital malformations including microcephaly, scoliosis, joint laxity, digital anomalies, as well as sometimes having autism spectrum disorder (ASD) and attention deficit hyperactivity disorder. Here, we report a boy with a 2.58‐Mb de novo deletion at chromosome 15q24. He is diagnosed with ASD and having multiple phenotypes similar to those reported in cases having 15q24 microdeletion syndrome. To delineate the critical genes and region that might be responsible for these phenotypes, we reviewed all previously published cases. We observe a potential minimum critical region of 650 kb (LCR15q24A‐B) affectingNEO1among other genes that might pertinent to individuals with ASD carrying this deletion. In contrast, a previously defined minimum critical region downstream of the 650‐kb interval (LCR15q24B‐D) is more likely associated with the developmental delay, facial dysmorphism, recurrent infection, and other congenital malformations. As a result, the ASD phenotype in this individual is potentially attributed by genes particularlyNEO1within the newly proposed critical region.
Excited‐State Aromaticity of Gold(III) Hexaphyrins and Metalation Effect Investigated by Time‐Resolved Electronic and Vibrational Spectroscopy
Authors: Kim Jinseok , Oh Juwon , Soya Takanori , Yoneda Tomoki , Park Seongchul , Lim Manho , Osuka Atsuhiro , Kim Dongho
Published: January 2020

Expanded porphyrins with appropriate metalation provide an excellent opportunity to study excited‐state aromaticity. The coordinated metal allows the excited‐state aromaticity in the triplet state to be detected through the heavy‐atom effect, but other metalation effects on the excited‐state aromaticity were ambiguous. Herein, the excited‐state aromaticity of gold(III) hexaphyrins through the relaxation dynamics was revealed via electronic and vibrational spectroscopy. The SQ states of gold [26]‐ and [28]‐hexaphyrins showed interconvertible absorption and IR spectra with those of counterparts in the ground‐state, indicating aromaticity reversal. Furthermore, while the T1 states of gold [28]‐hexaphyrins also exhibited reversed aromaticity according to Baird's rule, the ligand‐to‐metal charge‐transfer state of gold [26]‐hexaphyrins contributed by the gold metal showed non‐aromatic features arising from the odd‐number of π‐electrons.
Ruthenium‐Catalyzed Direct Asymmetric Reductive Amination of Diaryl and Sterically Hindered Ketones with Ammonium Salts and H2
Authors: Hu Le' an , Zhang Yao , Zhang Qing‐Wen , Yin Qin , Zhang Xumu
Published: January 2020

A Ru‐catalyzed direct asymmetric reductive amination of ortho‐OH‐substituted diaryl and sterically hindered ketones with ammonium salts is reported. This method represents a straightforward route toward the synthesis of synthetically useful chiral primary diarylmethylamines and sterically hindered benzylamines (up to 97 % yield, 93–>99 % ee). Elaborations of the chiral amine products into bioactive compounds and a chiral ligand were demonstrated through manipulation of the removable and convertible ‐OH group.
Anchored Mediator Enabling Shuttle‐Free Redox Mediation in Lithium‐Oxygen Batteries
Authors: Ko Youngmin , Park Hyunji , Lee Kyunam , Kim Sung Joo , Park Hyeokjun , Bae Youngjoon , Kim Jihyeon , Park Soo Young , Kwon Ji Eon , Kang Kisuk
Published: January 2020

Redox mediators (RMs) are considered an effective countermeasure to reduce the large polarization in lithium‐oxygen batteries. Nevertheless, achieving sufficient enhancement of the cyclability is limited by the trade‐offs of freely mobile RMs, which are beneficial for charge transport but also trigger the shuttling phenomenon. Here, we successfully decoupled the charge‐carrying redox property of RMs and shuttling phenomenon by anchoring the RMs in polymer form, where physical RM migration was replaced by charge transfer along polymer chains. Using PTMA (poly(2,2,6,6‐tetramethyl‐1‐piperidinyloxy‐4‐yl methacrylate)) as a polymer model system based on the well‐known RM tetramethylpiperidinyloxyl (TEMPO), it is demonstrated that PTMA can function as stationary RM, preserving the redox activity of TEMPO. The efficiency of RM‐mediated Li2O2 decomposition remains remarkably stable without the consumption of oxidized RMs or degradation of the lithium anode, resulting in an improved performance of the lithium‐oxygen cell.
Copper‐doped sulfonic acid‐functionalized MIL‐101(Cr) metal–organic framework for efficient aerobic oxidation reactions
Authors: Li Xiujuan , Zhou Zihao , Zhao Yuzhen , Ramella Daniele , Luan Yi
Published: January 2020

A series of Cr‐based metal–organic framework MIL‐101‐SO3H bearing sulfonic acid functional groups were utilized for the immobilization of catalytically active copper species via a post‐synthetic metalation method. The novel materials were fully characterized by scanning electron microscopy, X‐ray diffraction, energy dispersive X‐ray spectroscopy (EDX), X‐ray photoelectron spectroscopy (XPS), the Brunauer–Emmett–Teller method, and thermogravimetric analysis. XPS and the EDX element map both suggested that Cu2+ is coordinately bonded to the MIL‐101‐SO3H, which forms the MIL‐101‐SO3@Cu structure. The obtained copper‐doped MIL‐101‐SO3@Cu‐1, MIL‐101‐SO3@Cu‐2, and MIL‐101‐SO3@Cu‐3 catalysts were utilized in the selective oxidation of alcohols and epoxidation of olefins using molecular oxygen as an oxidant. Catalytic aerobic oxidation optimization showed that MIL‐101‐SO3@Cu‐1 is the optimal catalyst and it can be reused ten times without compromising the yield and selectivity.
Syntheses, structures, and properties of four coordination polymers based on 2,7‐di(pyridin‐4‐yl)‐9H‐fluoren‐9‐one
Authors: Liu Zhipeng , Wang Ming , Chen Kaixuan , Liu Baolin , Wang Dingkang , You Yujian , Zhou Xinhui , Huang Wei
Published: January 2020

Four coordination polymers (CPs), [Cd(2,7‐dpfo)2(NO3)2(CH3OH)]n (1), [Zn(2,7‐dpfo)(NO3)(CH3COO)]n (2), [Co(2,7‐dpfo)2(H2L)]n (3), and [Ni(2,7‐dpfo)2(H2L)]n (4) (where 2,7‐dpfo is 2,7‐di(pyridin‐4‐yl)‐9H‐fluoren‐9‐one and H4L is 1,1′:4′,1′′‐terphenyl‐4,2′,5′,4′′‐tetracarboxylic acid), were synthesized and structurally characterized. Compounds 1–4 were determined by elemental analyses, single crystal X‐ray diffraction analyses, powder X‐ray diffraction, infrared spectroscopy, and thermogravimetric analyses. Compound 1 displays a one‐dimensional (1D) zigzag chain structure, while compound 2 possesses a 1D ladder chain structure. Compounds 3 and 4 are isostructural and consist of 1D chains. The solid‐state luminescent properties of 1 and 2 and the magnetic properties of 3 and 4 were also investigated.
Synthesis, analytical and spectral characterization for new VO (II)‐triazole complexes; conformational study beside MOE docking simulation features
Authors: El‐Metwaly Nashwa , Farghaly Thoraya A. , Elghalban Marwa G.
Published: January 2020

New triazole‐derivatives were synthesized and characterized (spectral, analytical and conformational). After that, the new derivatives were coordinated with VO (II) atom to prepare new series of complexes. Distorted octahedral and square‐pyramidal geometries, were the geometries suggested based on UV‐ Vis and ESR spectra. A neutral poly‐dentate mode of bonding was proposed by 1:1 (M:L), for all complexes. TGA study supports the molecular formula of VO (II) complexes as well as, mass spectral‐analysis that executed for examples. The isotropic, anisotropic, molecular orbital and Hamiltonian parameters were estimated upon ESR spectra, for selected complexes. XRD patterns were executed for three complexes, two among appeared with particulate‐sizes in nanometer‐range. Conformational study was executed for all synthesizes applying RTD‐B3LYP‐FC method. Essential physical parameters were estimated and discussed. MOE‐docking that considered a bright part, was performed over all compounds towards 3s7s and 5jm5, as functional tumor proteins. The docking interaction parameters, introduced strongly some synthesizes to be anti‐tumor agents.
Inverse electron‐demand Diels‐Alder (iEDDA) bioorthogonal conjugation of half‐sandwich transition metallocarbonyl entities to a model protein
Authors: Jamroz Daria , Fischer‐Durand Nathalie , Palusiak Marcin , Wojtulewski Sławomir , Jarzyński Szymon , Stępniewska Marlena , Salmain Michèle , Rudolf Bogna
Published: January 2020

Novel transition metallocarbonyl complexes carrying a norbornene or an oxanorbornene group were synthesized by [4 + 2] cycloaddition between the organometallic maleimide dienophiles and cyclopentadiene or furan, respectively. The oxanorbornene adduct was obtained as a mixture of endo and exo isomers as confirmed by X‐ray diffraction and NMR spectroscopy. The (oxa)norbornene groups further provided convenient chemical reporters to carry out inverse electron demand Diels‐Alder (iEDDA) reactions with tetrazine derivatives. Detailed kinetic studies with a model tetrazine revealed that faster rates of reaction were determined with both isomers of the oxanorbornene complex with respect to the norbornene complexes. Eventually, incorporation of metallocarbonyl entities into bovine serum albumin equipped with tetrazine handles was achieved as shown by IR spectroscopy of the protein conjugates.
Is the existence of a mutualistic relationship between Lobesia botrana and Botrytis cinerea well‐founded?
Authors: Kiaeian Moosavi Fatemeh , Cargnus Elena , Torelli Emanuela , Bortolomeazzi Renzo , Zandigiacomo Pietro , Pavan Francesco
Published: January 2020

Some studies have highlighted benefits for Lobesia botrana by adding Botrytis cinerea mycelium to an artificial larval diet and have suggested a mutualistic relationship between the two organisms on grapevine, hypothesizing that fungal sterols were the nutritional factor involved. Because the nutritional quality of an artificial diet should be similar to grapes to allow extrapolation of the results to the field conditions, in the current study L. botrana larval performance was compared when larvae were fed on grapes (berries) or two artificial diets either with or without enrichment with B. cinerea. Based on sterol analysis, the two artificial diets had high cholesterol content, but relative to berries showed comparable and low phytosterol contents, respectively (high‐ and low‐phytosterol, HPh, and LPh). While larval fitness on the HPh diet was similar to berries, the LPh diet led to higher mortality and worse larval performance. The addition of the fungus compensated for the shortage in the LPh diet but did not improve the HPh diet. Supplementing the LPh diet with linoleic acid, which is supplied also from B. cinerea, partially improved larval performance. In a field experiment, females did not show any egg‐laying preferences towards naturally botrytized bunches. The positive effect of B. cinerea on the moth's next generation that is reported in the literature could be a consequence of fungus developed inside berry tunnels bored by larvae. Therefore, based on our data and previous reports the existence of a mutualistic relationship between L. botrana and B. cinerea is not well‐founded.
An accessible, agile and low‐cost workflow for 3D virtual analysis and automatic vector tracing of engravings: Atlantic rock art analysis
Authors: Gil‐Docampo Mariluz , Peña‐Villasenín Simón , Ortiz‐Sanz Juan
Published: January 2020

In recent years, three‐dimensional (3D) modelling with photogrammetry and enhancement methods from computer graphics communities have been used with excellent results for studies of rock art engravings. However, despite their abundance, most Atlantic rock art elements in the Iberian Peninsula have not yet been geometrically documented in 3D. The aims of this study include deepening the application of imaged‐based modelling, digital 3D model post‐processing, and diffusion tools in determining an accessible and straightforward workflow that is accessible for amateur and professional rock art researchers. The proposed workflow makes possible the prospection, documentation, enhancement, and diffusion of this heritage phenomenon in a massive collaborative manner. Thus, a representative sample of Atlantic rock art was documented using an affordable and time‐optimized methodology for image‐based modelling with free software at all stages of the process. This methodology improves the promotion of documentation of heritage through professional and social collaboration. The diffusion can be performed from two‐dimensional (2D) vectorizations from the rendering of MeshLab Radiance Scaling enhancement and automatic vectorizers or from the direct publication of enhanced 3D models, which are currently possible with platforms such as Sketchfab.
Speed observer of induction machine based on backstepping and sliding mode for low‐speed operation
Authors: Morawiec Marcin , Lewicki Arkadiusz , Wilczyński Filip
Published: January 2020

This paper presents a speed observer design based on backstepping and sliding mode approaches. The inputs to the observer are the stator current and the voltage vector components. This observer structure is extended to the integrators. The observer stabilizing functions contain the appropriate sliding surfaces which result from the Lyapunov function. The rotor angular speed is obtained from the non‐adaptive formula with a sliding mode mechanism. It allows improvement of the robustness of parameters uncertainties and the zero rotor speed to work (near to the unobservable region). In the sensorless control system, the classical first‐order sliding‐mode controllers are applied with the transformation of the multi‐scalar variable. The proposed control system structure can be named full‐decoupled due to multi‐scalar variables transformation and the feedback control law obtained from the Lyapunov theorem. The theoretical derivations are verified in experimental waveforms. The sensorless control system's robustness is verified in the experimental investigations by using the nominal machine parameters uncertainties method.
On the tracking of fast trajectories of a 3DOF torsional plant: A flatness based ADRC approach
Authors: Ramírez‐Neria Mario , Gao Zhiqiang , Sira‐Ramirez Hebertt , Garrido‐Moctezuma Ruben , Luviano‐Juarez Alberto
Published: January 2020

In this article, a highly oscillatory 3 degrees of freedom (DOF) torsional plant is used to demonstrate the effectiveness of the combined differential flatness property and active disturbance rejection control (ADRC) methodology in the output tracking of fast reference trajectory and vibration suppression problems. The controller design is synthesized in the absence of detailed knowledge of the system model, which means that the resonant modes are essentially unknown to the designer. Experimental results confirm that the excellent rest‐to‐rest trajectory tracking performance is attained while permanently attenuating remaining vibrations in all the three disks.
Exploring Cage‐warped Rotation Isomers of C20 Fullerene: MP2 and Density Functional Calculations
Authors: Lee Jangwon , Cho Yongjae , Jang MinJeong , Kook GaYoung , Gho HeeSu , Lee Changhoon , Hoang Geun C. , Lee Kee Hag
Published: January 2020

Using the density functional methods B3LYP, M06‐2X, PBE1PBE, B3LYP D3, M06‐2X D3, and PBE1PBE D3, and the ab initio MP2 calculations, the optimized atomic structures and energies of C20 cage rotation isomers without a constraint were obtained. The reaction path between the two rotational isomers was then studied, in which there are three local stable atomic structures. One is the most stable fullerene structure with the D2h point group staggered between the upper and bottom pentagons (ST) and the other is the second lowest energy rotational isomer with the Cs point group eclipsed between the upper and bottom pentagons (EC) with a torn fullerene structure (M1) between ST and EC. The first transition structure T1 between the ST and the M1, and the second transition structure T2 between the M1 and the EC were then obtained along the reaction coordinate between these three structures. Vibration analysis of all optimized structures including the transition structures without a constraint was carried out. For each of the rotational isomers obtained by our calculations, thermodynamic stability was explained with the relative energy difference, and then the kinetic stability was analyzed as the HOMO–LUMO energy difference.
Fabrication and Characterization of MWCNTs by Syngas and Temperature Conditions
Authors: Park Suyoung , Kim Sangwoo , Na Han Gil , Choi Sun‐Woo , Jin Changhyun
Published: January 2020

The morphologies, bulk densities, and synthesis yields of multi‐walled carbon nanotubes (MWCNTs) were analyzed by optimizing the catalyst, syngas, and synthesis temperature, which are key factors in the production of MWCNTs. In addition, MWCNTs were applied to polymer composites, and their electrical conductivities were evaluated through surface resistance measurements. The catalyst used in this process was a deposition precipitation method that offers favorable uniformity of loading through the liquid phase process and provides the advantage of controlling the shape using a support. Furthermore, physical and electrical analyses were performed in the range from 650 to 725°C using ethylene, butane, and liquefied petroleum gas (LPG) syngas. The results showed that the optimal synthesis yield and electrical conductivity of ethylene and butane were observed at 675°C, while those of LPG syngas were observed at 700°C. This implies that the aggregate diameter and bundle length tend to decrease under the most optimal conditions.
Retracted: Long non‐coding RNA ARAP1‐AS1 promotes tumorigenesis and metastasis through facilitating proto‐oncogene c‐Myc translation via dissociating PSF/PTB dimer in cervical cancer
Authors: Zhang Yao , Wu Dan , Wang Dian
Published: January 2020

Long non‐coding RNA (lncRNA) is emerging as a pivotal regulator in tumorigenesis and aggressive progression. Here, we focused on an oncogenic lncRNA, ARAP1 antisense RNA 1 (ARAP1‐AS1), which was notably upregulated in cervical cancer (CC) tissues, cell lines and serum. High ARAP1‐AS1 expression was closely associated with larger tumor size, advanced FIGO stage as well as lymph node metastasis. Importantly, it was identified as an effective diagnostic and prognostic biomarker for CC. In vitro and in vivo assays showed that knockdown of ARAP1‐AS1 inhibited, while overexpression of ARAP1‐AS1 promoted CC cell growth and dissemination. Stepwise mechanistic dissection unveiled that ARAP1‐AS1 could directly interact with PSF to release PTB, resulting in accelerating the internal ribosome entry site (IRES)‐driven translation of proto‐oncogene c‐Myc, thereby facilitating CC development and progression. Moreover, c‐Myc was able to transcriptionally activate ARAP1‐AS1 by directly binding to the E‐box motif located on ARAP1‐AS1 promoter. Taken together, our findings clearly reveal the crucial role of ARAP1‐AS1 in CC tumorigenesis and metastasis via regulation of c‐Myc translation, targeting ARAP1‐AS1 and its related regulatory loop implicates the therapeutic possibility for CC patients.
A New One‐Pot Fluorescence Derivatization Strategy for Highly Sensitive MicroRNA Analysis
Authors: Pan Li , Zhang Huaisheng , Zhao Jingjin , Ogungbe Ifedayo Victor , Zhao Shulin , Liu Yi‐Ming
Published: January 2020

MicroRNAs (miRNAs) modulate the expression of over 30 % of mammalian genes during development and apoptosis, and abnormal expression of miRNAs may lead to a range of human pathologies. Therefore, analysis of miRNAs is valuable for disease diagnostics. In this work, a novel one‐pot fluorescence derivatization strategy was developed for miRNA analysis. The mechanism of the derivatization reaction was explored by using instrumental methods, including liquid chromatography, fluorescence spectroscopy, and mass spectrometry. Highly fluorescent N6‐ethenoadenine (ϵ‐adenine) was formed and detached from the miRNA sequence through the reaction of adenine in nucleic acids with 2‐chloroacetaldehyde (CAA) at 100 °C. This is the first experimental evidence that the cooperation of formed ϵ‐adenine and water‐mediated hydrogen‐bond interaction between the proton at the 2′‐ and the oxyanion at 3′‐positions stabilized the oxocarbenium significantly, which makes the depurination and derivatization of miRNA highly effective. Based on this derivatization strategy, a facile and sensitive high‐performance liquid chromatography method was developed for quantitative assay of miRNAs. In combination with magnetic solid‐phase extraction (MSPE), the HPLC method was shown to be useful for the determination of microRNAs at sub‐picomolar level in serum samples.
Visible‐Light‐Mediated Click Chemistry for Highly Regioselective Azide–Alkyne Cycloaddition by a Photoredox Electron‐Transfer Strategy
Authors: Wu Zheng‐Guang , Liao Xiang‐Ji , Yuan Li , Wang Yi , Zheng You‐Xuan , Zuo Jing‐Lin , Pan Yi
Published: January 2020

Click chemistry focuses on the development of highly selective reactions using simple precursors for the exquisite synthesis of molecules. Undisputedly, the CuI‐catalyzed azide–alkyne cycloaddition (CuAAC) is one of the most valuable examples of click chemistry, but it suffers from some limitations as it requires additional reducing agents and ligands as well as cytotoxic copper. Here, we demonstrate a novel strategy for the azide–alkyne cycloaddition reaction that involves a photoredox electron‐transfer radical mechanism instead of the traditional metal‐catalyzed coordination process. This newly developed photocatalyzed azide–alkyne cycloaddition reaction can be performed under mild conditions at room temperature in the presence of air and visible light and shows good functional group tolerance, excellent atom economy, high yields of up to 99 %, and absolute regioselectivity, affording a variety of 1,4‐disubstituted 1,2,3‐triazole derivatives, including bioactive molecules and pharmaceuticals. The use of a recyclable photocatalyst, solar energy, and water as solvent makes this photocatalytic system sustainable and environmentally friendly. Moreover, the azide–alkyne cycloaddition reaction could be photocatalyzed in the presence of a metal‐free catalyst with excellent regioselectivity, which represents an important development for click chemistry and should find versatile applications in organic synthesis, chemical biology, and materials science.