bluuebunny/crossref_metadata_2025 huggingface dataset:
Development of a prognostic scoring model for predicting the survival of elderly patients with hepatocellular carcinoma
Authors: Wan Sizhe , Nie Yuan , Zhu Xuan
Published: February 2020

Background

The number of elderly hepatocellular carcinoma (HCC) patients is increasing, and precisely assessing of the prognosis of these patients is necessary. We developed a prognostic scoring model to predict survival in elderly HCC patients.

Methods

We extracted data from 4,076 patients ≥65 years old from the Surveillance, Epidemiology, and End Results (SEER) database and randomly divided them into training and validation groups. Cox regression analysis was used to screen for meaningful independent prognostic factors. The receiver operating characteristic curve reflected the model’s discrimination power.

Results

Age, race, American Joint Committee on Cancer stage, degree of tumour differentiation, tumour size, alpha-fetoprotein and tumour therapy were independent prognostic factors for survival in elderly HCC patients. We developed a prognostic scoring model based on the seven meaningful variables to predict survival in elderly HCC patients. The AUCs of the model were 0.805 (95% CI [0.788–0.821]) and 0.788 (95% CI [0.759–0.816]) in the training and validation groups, respectively. We divided the patients into low-risk groups and high-risk groups according to the optimal cut-off value. The Kaplan–Meier survival curve showed that in the training and validation groups, the survival rate of the low-risk group was significantly higher than that of the high-risk group (P < 0.001).

Conclusion

Based on a large population, we constructed a prognostic scoring model for predicting survival in elderly HCC patients. The model may provide a reference for clinicians for preoperative and postoperative evaluations of elderly HCC patients.
Spatial Mapping of Measles-Rubella Campaign in a Rural Area near Bengaluru, Karnataka, India
Authors: Ramesh Masthi N. R. , Jahan Afraz
Published: February 2020

Immunization is an important public health intervention. The Measles-Rubella (MR) campaign was launched during 2017 in India for the elimination of measles. This study explored vaccination coverage and spatial mapping using QGIS and Google Earth Pro. WHO-EPI 30 clusters sampling technique for evaluation of vaccination coverage was performed in villages within the rural area of a Medical College near Bengaluru. Seven children aged 2-15 years were surveyed per cluster, resulting in 210 children. Smartphones having GPS/Garmin GPS72H (handheld GPS receiver) were used for noting coordinates. Subsequently all these coordinates were plotted for spatial mapping of vaccination coverage. The geospatial characteristics of the households surveyed were described using spatial mapping. Results indicate that 87.6% were immunized with MR Vaccine under the campaign, but 12.4% remained unimmunized, the reasons given being absence, ignorance, or refusal because of rumours concerning side-effects. The Measles-Rubella campaign coverage was found to be satisfactory. In addition the spatial mapping is a useful tool for measurement of coverage of a vaccination campaign. There was no clustering of unimmunized subjects observed on spatial mapping.
A Comparative Study on the Developmental Trends in the Contemporary Iranian Architecture; Case Study-Khosrawi Leather Factory of Tabriz
Authors: Mahmoudi Shayan , Rezvani Ali , Niknam Mehdi
Published: February 2020

Architecture and urbanization are representatives of our architectural and cultural histories. Many of the lost historical characteristics can come out of the back door citing such representatives. Reconstruction and restoration are a set of activities that deal with the body and spirit of a subject. The subject can be a city, a natural environment or an architectural structure. There are different approaches to reconstruction and restoration, which differ significantly in terms of the level of intervention in a historical subject. This is a technique that our archaeologists are not sufficiently familiar with. From an archaeological point of view on the historical subjects, any document could not be as consistent as the architectural works with the circumstances of the community. The nature of the art of modern history is to see which cases have not been addressed in historical documents. As the historical subjects’ evidence, we were not so diligent in the preservation of such subjects as a documentary. The aim of this study is to investigate the heritage of contemporary architecture and to determine how to preserve such works, as well as to review the Khosrawi leather factory in Tabriz, which has now maintained its role as the Islamic Art University. The results of this research, which are obtained through a descriptive-analytical method, show that we can preserve the architectural structures by changing the application of traditional structures to the cultural or social ones.
Robust fault‐tolerant control for discrete‐time switched systems with time delays
Authors: Telbissi Kenza , Benzaouia Abdellah
Published: February 2020

This study outlines the problem of active fault‐tolerant control for delayed discrete‐time switched systems. Using switched proportional‐integral observer and multiple Lyapunov‐Krasovski function, less conservative sufficient conditions are established to design a robust fault estimation (FE) algorithm via linear matrix inequality form. Afterward, a fault‐tolerant performance is realized based on this fast and exact FE information to compensate the effect of actuator fault while stabilizing the closed‐loop system. The efficiency of the proposed strategy is proved through simulation examples and comparison results.
Ambient‐Dried, 3D‐Printable and Electrically Conducting Cellulose Nanofiber Aerogels by Inclusion of Functional Polymers
Authors: Françon Hugo , Wang Zhen , Marais Andrew , Mystek Katarzyna , Piper Andrew , Granberg Hjalmar , Malti Abdellah , Gatenholm Paul , Larsson Per A. , Wågberg Lars
Published: February 2020

This study presents a novel, green, and efficient way of preparing crosslinked aerogels from cellulose nanofibers (CNFs) and alginate using non‐covalent chemistry. This new process can ultimately facilitate the fast, continuous, and large‐scale production of porous, light‐weight materials as it does not require freeze‐drying, supercritical CO2 drying, or any environmentally harmful crosslinking chemistries. The reported preparation procedure relies solely on the successive freezing, solvent‐exchange, and ambient drying of composite CNF‐alginate gels. The presented findings suggest that a highly‐porous structure can be preserved throughout the process by simply controlling the ionic strength of the gel. Aerogels with tunable densities (23–38 kg m−3) and compressive moduli (97–275 kPa) can be prepared by using different CNF concentrations. These low‐density networks have a unique combination of formability (using molding or 3D‐printing) and wet‐stability (when ion exchanged to calcium ions). To demonstrate their use in advanced wet applications, the printed aerogels are functionalized with very high loadings of conducting poly(3,4‐ethylenedioxythiophene):tosylate (PEDOT:TOS) polymer by using a novel in situ polymerization approach. In‐depth material characterization reveals that these aerogels have the potential to be used in not only energy storage applications (specific capacitance of 78 F g−1), but also as mechanical‐strain and humidity sensors.
Steric Impediment of Ion Migration Contributes to Improved Operational Stability of Perovskite Solar Cells
Authors: Tan Shaun , Yavuz Ilhan , De Marco Nicholas , Huang Tianyi , Lee Sung‐Joon , Choi Christopher S. , Wang Minhuan , Nuryyeva Selbi , Wang Rui , Zhao Yepin , Wang Hao‐Cheng , Han Tae‐Hee , Dunn Bruce , Huang Yu , Lee Jin‐Wook , Yang Yang
Published: February 2020

The operational instability of perovskite solar cells (PSCs) is known to mainly originate from the migration of ionic species (or charged defects) under a potential gradient. Compositional engineering of the “A” site cation of the ABX3 perovskite structure has been shown to be an effective route to improve the stability of PSCs. Here, the effect of size‐mismatch‐induced lattice distortions on the ion migration energetics and operational stability of PSCs is investigated. It is observed that the size mismatch of the mixed “A” site composition films and devices leads to a steric effect to impede the migration pathways of ions to increase the activation energy of ion migration, which is demonstrated through multiple theoretical and experimental evidence. Consequently, the mixed composition devices exhibit significantly improved thermal stability under continuous heating at 85 °C and operational stability under continuous 1 sun illumination, with an extrapolated lifetime of 2011 h, compared to the 222 h of the reference device.
The Inside‐Outs of Metal Hydride Dehydrogenation: Imaging the Phase Evolution of the Li‐N‐H Hydrogen Storage System
Authors: White James L. , Baker Alexander A. , Marcus Matthew A. , Snider Jonathan L. , Wang Timothy C. , Lee Jonathan R. I. , Kilcoyne David A. L. , Allendorf Mark D. , Stavila Vitalie , El Gabaly Farid
Published: February 2020

Complex metal hydrides provide high‐density hydrogen storage, which is essential for vehicular applications. However, the practical application of these materials is limited by thermodynamic and kinetic barriers present during the dehydrogenation and rehydrogenation processes as new phases form inside parent phases. An improved understanding of the mixed‐phase mesostructures and their interfaces will assist in improving cyclability. In this work, the phase evolution during hydrogenation of lithium nitride and dehydrogenation of lithium amide with lithium hydride is probed with scanning transmission X‐ray microscopy at the nitrogen K edge. With this technique, core–shell structures are observed in particles of both partially hydrogenated Li3N and partially dehydrogenated LiNH2 + 2LiH. To generate these structures, the rate‐limiting step must shift from internal hydrogen diffusion during hydrogenation to the formation of hydrogen gas at the surface during desorption.
Ion Sputtering–Assisted Double‐Side Interfacial Engineering for CdIn2S4 Photoanode toward Improved Photoelectrochemical Water Splitting
Authors: Xu Weiwei , Tian Wei , Meng Linxing , Cao Fengren , Li Liang
Published: February 2020

Due to its suitable band energy level and small band gap, CdIn2S4 is a promising photoanode for photoelectrochemical (PEC) water splitting. Nevertheless, the serious charge recombination at the back contact and photoelectrode/electrolyte interface severely hinders its PEC activity. Herein, a facile magnetron ion‐sputtering strategy is adopted to fabricate TiO2 underlayer and NiO overlayer to modify both sides of CdIn2S4 photoanode. The TiO2 underlayer serves as an electron transport layer to promote electrons transfer from CdIn2S4 to fluorine‐doped tin oxide substrate and hinder holes' transportation, thus suppressing the charge recombination at the back contact. NiO, as a p‐type semiconductor, forms a p‐n heterojunction with CdIn2S4, inducing a built‐in electric field to facilitate charge transport. Meanwhile, NiO overlayer acts as a co‐catalyst to enhance surface reaction kinetics, and thereby improves the carrier injection efficiency at photoelectrode/electrolyte interface. As a result, the optimum TiO2/CdIn2S4/NiO photoanode exhibits photocurrent as high as 0.6 mA cm−2 at 1.23 V versus reversible hydrogen electrode, which is about 2.3 times that of bare CdIn2S4. This work provides an effective strategy to manipulate the charge carrier dynamics to improve the PEC activity of photoanode.
Divergent Reaction Pathways of β‐Chlorovinyl Ketones: Microwave‐Assisted Thermal Nazarov Cyclization versus Cycloisomerization via Soft Vinyl Enolization
Authors: Kim Hun Young , Oh Kyungsoo
Published: February 2020

Divergent reaction pathways of β‐chlorovinyl ketones have been established to provide stereodefined alkylidenecyclopent‐2‐enones and 2‐alkenylfuran derivatives. The switch of the reaction pathways was made possible by the microwave‐assisted thermal Nazarov cyclization reaction of β‐chlorovinyl ketones, whereas the soft α‐vinyl enolization of β‐chlorovinyl ketones allowed the generation of allenyl ketone intermediates that in turn smoothly underwent cycloisomerization to the 2‐alkenyl furan derivatives in good to excellent yields.

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Photophysics of Methylammonium Lead Tribromide Perovskite: Free Carriers, Excitons, and Sub‐Bandgap States
Authors: Droseros Nikolaos , Tsokkou Demetra , Banerji Natalie
Published: February 2020

Methylammonium lead tribromide perovskite, one of the first artificially synthesized perovskites, can be used in multijunction solar cells and for light‐emitting applications. Its structure leads to a wide direct bandgap, a high extinction coefficient for absorption, and an exciton binding energy that is higher than the thermal energy at room temperature. The broad range of studies performed on the optical phenomena in this material has revealed the contribution of free carriers, excitons, and defect states to its photoluminescence properties. The present report aims to highlight the role played by the different primary photoexcitations, by defects and a variety of optical phenomena (dual emission, reabsorption, photon‐recycling, Rashba‐splitting) on the observed excited‐state properties of this semiconductor. Focus is given to the manifestation of these properties in different spectroscopic measurements.
Relationships of protein composition, gluten structure, and dough rheological properties with short biscuits quality of soft wheat varieties
Authors: Zheng Baoqiang , Zhao Hong , Zhou Qin , Cai Jian , Wang Xiao , Cao Weixing , Dai Tingbo , Jiang Dong
Published: February 2020

Understanding the contribution of protein composition and gluten structure to dough property and biscuit baking is crucial to improve soft wheat (Triticum aestivum L.) grain quality. Thus, the relationships of protein composition, gluten structure, and dough rheological properties with short biscuits quality was investigated using 10 Chinese soft wheat varieties. Content of grain protein, flour protein, gliadin, glutenin, and high and low molecular weight glutenin subunits were significantly positively correlated with hardness of biscuit, but negatively correlated with spread factor and sensory score. Gluten of wheat varieties with lower dough strength and better biscuit quality showed thinner walls of apertures and more regular apertures in its microstructure. The gluten with higher strength had more apertures and antiparallel β‐sheets and fewer α‐helices. Moreover, dough with a higher softening degree was easier to stretch and tended to produce biscuits with larger diameter and crispier taste during baking. In conclusion, main wheat quality characteristics that can be used to select grain samples suitable for making tasty biscuits were recommended as follows: flour protein content, wet gluten content and microstructure, Zeleny sedimentation value, and dough softening degree.
In vitro and In silico Studies on the Base Effect in Palladium‐Catalyzed Direct Arylation
Authors: Lai Yu‐Ying , Yang Hau‐Ren , Lee Hao‐Ting , Tsai Tien‐Liang , Sun Han‐Sheng
Published: February 2020

Palladium‐catalyzed direct‐arylation (DAr) has shown promise in synthesizing conjugated molecules and polymers. Herein, palladium‐catalyzed DAr reactions of 2‐bromo‐3‐alkyl‐thiophene in the presence of distinct bases including pivalate, acetate, carbonate, and hydroxide, are performed in vitro and in silico. The entire pathways comprising oxidative addition (OA), concerted metalation‐deprotonation (CMD), and reductive elimination (RE) are investigated theoretically, indicating that the rate‐determining step varies with the base. Natural bond orbital analysis on the CMD transition states reveals that the classical Lewis pair and frustrated Lewis pair play important roles in the base‐coordinated CMD and the base‐assisted CMD, respectively. Multivariate regression analysis between the calculated CMD activation barrier and the orbital interactions yields a model equation, which is employed to further elucidate the characters of Lewis acid and Lewis base in the CMD. Overall, the computational results from the present study are in agreement with the experimental reaction yields and constitute the interpretation of the working principles for the DAr catalytic system, shedding light on further optimization and advance.
Exploiting N−H–π Interactions in 2‐(Dimesitylboraneyl)‐1H‐pyrrole for Luminescence Enhancement
Authors: Kalluvettukuzhy Neena K , Pagidi Sudhakar , Prasad Nandi Rajendra , Thilagar Pakkirisamy
Published: February 2020

Design and development of stable blue emitters are challenging owing to their potential applications in displays and lighting technologies. Triarylborane (TAB) with suitable donors has been extensively exploited in several fields. We report herein the synthesis and structural characterization of a simple 2‐(dimesitylboryl)‐1H‐pyrrole (2) and its precursor N‐Boc‐(dimesitylboryl)‐pyrrole (1). In the crystal lattice of 2, supramolecular dimer was formed by strong N−H–π (2.59 Å) hydrogen bonding interactions between the monomers and this dimer is further connected by weak van der Waals interactions (C−H–π) with neighbouring dimers to form a supramolecular network. There is no solvatochromism noted in the absorption spectra, however significant positive solvatochromism was observed in the fluorescence spectra; points to the polar nature of excited state of 1 and 2. Compound 2 showed intense and efficient blue color luminescence in the solid state than that of 1. Thus, N−H–π interactions and π‐excessive nature of pyrrole are responsible for the above features. Impressively, compounds 1 and 2 exhibit the phosphorescence emission with a long‐lived lifetime of ∼0.55 s at 77 K and delayed fluorescence at room temperature. DFT/TD‐DFT calculations were performed to support the experimental observations.
Do Serum Urate–Associated Genetic Variants Differentially Contribute to Gout Risk According to Body Mass Index? Analysis of the UK Biobank
Authors: Tai Vicky , Narang Ravi K. , Gamble Greg , Cadzow Murray , Stamp Lisa K. , Merriman Tony R. , Dalbeth Nicola
Published: February 2020

Objective

To examine whether urate‐associated genetic variants differ in their influence on gout risk according to body mass index (BMI).

Methods

This research was conducted using the UK Biobank Resource (n = 358,728). Participants were divided into 3 groups: BMI <25 kg/m2 (low/normal), BMI ≥25 kg/m2–<30 kg/m2 (overweight), and BMI ≥30 kg/m2 (obese). Gene–BMI interactions for gout association were tested by logistic regression using a urate genetic risk score (GRS).

Results

Compared to participants with a GRS less than the mean, the prevalence of gout was higher in those with a GRS greater than or equal to the mean in the low/normal BMI group (0.27% versus 0.77%), in the overweight BMI group (1.02% versus 3.02%), and in the obese BMI group (2.49% versus 6.23%). A GRS greater than or equal to the mean was positively associated with gout compared to a GRS less than the mean in the low/normal BMI group (odds ratio [OR] 2.89 [95% confidence interval (95% CI) 2.42–3.47]), in the overweight BMI group (OR 3.09 [95% CI 2.84–3.36]), and in the obese BMI group (OR 2.65 [95% CI 2.46–2.86]). There was a mildly attenuated effect of the GRS on gout risk in the obese BMI group compared to the overweight BMI group, but no difference in the effect of the GRS between the low/normal BMI and overweight BMI groups, nor between the low/normal BMI and obese BMI groups.

Conclusion

The association of a urate GRS with gout is mildly attenuated in obese individuals compared to overweight individuals. However, genetic variants have a strong effect on gout risk in those with overweight and obese BMIs, with an effect similar to that observed in low/normal BMI.
One‐Pot Cascade Biotransformation for Efficient Synthesis of Benzyl Alcohol and Its Analogs
Authors: Liu Lijun , Zhu Yuling , Chen Yufen , Chen Huiyu , Fan Cong , Mo Qiwen , Yuan Jifeng
Published: February 2020

Benzyl alcohol is a naturally occurring aromatic alcohol and has been widely used in the cosmetics and flavor/fragrance industries. The whole‐cell biotransformation for synthesis of benzyl alcohol directly from bio‐based L‐phenylalanine (L‐Phe) was herein explored using an artificial enzyme cascade in Escherichia coli. Benzaldehyde was first produced from L‐Phe via four heterologous enzymatic steps that comprises L‐amino acid deaminase (LAAD), hydroxymandelate synthase (HmaS), (S)‐mandelate dehydrogenase (SMDH) and benzoylformate decarboxylase (BFD). The subsequent reduction of benzaldehyde to benzyl alcohol was achieved by a broad substrate specificity phenylacetaldehyde reductase (PAR) from Solanum lycopersicum. We found the designed enzyme cascade could efficiently convert L‐Phe into benzyl alcohol with conversion above 99%. In addition, we also examined L‐tyrosine (L‐Tyr) and m‐fluoro‐phenylalanine (m‐f‐Phe) as substrates, the cascade biotransformation could also efficiently produce p‐hydroxybenzyl alcohol and m‐fluoro‐benzyl alcohol. In summary, the developed biocatalytic pathway has great potential to produce various high‐valued fine chemicals.
Room‐Temperature Phosphorescence‐active Boronate Particles: Characterization and Ratiometric Afterglow‐sensing Behavior by Surface Grafting of Rhodamine B
Authors: Hoshi Mitsuki , Nishiyabu Ryuhei , Hayashi Yuichiro , Yagi Shigeyuki , Kubo Yuji
Published: February 2020

We found that boronate particles (BP), as a self‐assembled system prepared by sequential dehydration of benzene‐1,4‐diboronic acid with pentaerythritol, showed greenish room‐temperature phosphorescence (RTP). This emission was observed in both solid and dispersion state in water. To understand the RTP properties, X‐ray crystallographic analysis, and density functional theory (DFT) and time‐dependent DFT at M06‐2X/6‐31G(d,p) level were performed using 3,9‐dibenzo‐2,4,8,10‐tetraoxa‐3,9‐diboraspiro[5.5]undecane (1) as a model compound. Our interest in functionalizing the RTP‐active particles led us to graft Rhodamine B onto their surface. The resulting system emitted a dual afterglow via a Förster‐type resonance energy transfer process from the BP in the excited triplet state to Rhodamine B acting as an acceptor fluorophore. This emission behavior was used for ratiometric afterglow sensing of water content in THF with a detection limit of 0.28 %, indicating that this study could pave the way for a new strategy for developing color‐variable afterglow chemosensors for various analytes.
Proton‐Activated Amorphous Room‐Temperature Phosphorescence for Humidity Sensing and High‐Level Data Encryption
Authors: Deng Yuchen , Li Peng , Sun Shujuan , Jiang Haiyan , Ji Xu , Li Huanrong
Published: February 2020

Supramolecular co‐assembling terpyridine‐derivatives with nanoclay (LP) are exploited to acquire efficient amorphous room‐temperature phosphorescence (RTP). Experimental and theoretical investigations reveal that this co‐assembly not only brings about a configuration transformation from the trans‐trans (a) to the cis‐trans (a′′) form via the protonating process, significantly narrowing the singlet‐triplet energy gap, thereby effectively facilitating the single‐triplet ISC processes, but also well protects the triplet state and suppresses the nonradiative transitions via restricting molecular rotation and vibration by the hydrogen‐bond interactions between them. Additionally, the flexible and transparent films, through co‐assembling1@LP(or2@LP) with polyvinyl alcohol (PVA), also display excellent phosphorescence performance. Owing to their distinctive RTP performances, the RH sensing and high‐level data encryption are achieved.
Rhodium(III)‐Catalyzed Redox‐Neutral Coupling of α‐Trifluoromethylacrylic Acid with Benzamides through Directed C−H Bond Cleavage
Authors: Yoshimoto Risa , Usuki Yoshinosuke , Satoh Tetsuya
Published: February 2020

A rhodium(III)‐catalyzed redox‐neutral coupling of α‐trifluoromethylacrylic acid with bezamides proceeds smoothly accompanied by amide‐directed C−H bond cleavage to produce β‐[2‐(aminocarbonyl)phenyl]‐α‐trifluoromethylpropanoic acid derivatives. One of the products can be transformed to a trifluoromethyl substituted heterocyclic compound. In addition, the redox‐neutral coupling of α‐trifluoromethylacrylic acid with related aromatic substrates possessing a nitrogen‐containing directing group can also be conducted under similar conditions.
Molecular Recognition of Zwitterions with Artificial Receptors
Authors: Alfonso Ignacio , Solà Jordi
Published: February 2020

Many biomolecules exist as internal ion pairs or zwitterions within a biologically relevant pH range. Despite their importance, the molecular recognition of this type of systems is specially challenging due to their strong solvation in aqueous media, and their trend to form folded or self‐assembled structures by pairing of charges of different sign. In this Minireview, we will discuss the molecular recognition of zwitterions using non‐natural, synthetic receptors. This contribution does not intend to make a full in‐depth revision of the existing research in the field, but a personal overview with selected representative examples from the recent literature.
Controlled Synthesis of Cr‐Co0.85Se Nanoarrays for Water Splitting at an Ultralow Cell Voltage of 1.43 V
Authors: Du Xiaoqiang , Fu Jianpeng , Zhang Xiaoshuang
Published: February 2020

Water splitting has attracted more and more attention as a promising strategy for the production of clean hydrogen fuel. In this work, a new synthesis strategy was proposed, and Co0.85Se was synthesized on nickel foam as the main matrix. The doping of appropriate Cr amount into the target of Co0.85Se and the Cr‐Co0.85Se resulted in an excellent electrochemical performance. The doping of Cr introduces Cr3+ ions which substitute Co2+ and Co3+ ions in Co0.85Se, so that the lattice parameters of the main matrix were changed. It is worth noting that the Cr0.15‐Co0.85Se/NF material exhibits an excellent performance in the oxygen evolution reaction (OER) test. When the current density reaches 50 mA cm−2 for OER, the overpotential is only 240 mV. For the hydrogen evolution reaction (HER) tests, the overpotential is only 117 mV to drive 10 mA cm−2 of current density. Moreover, when the Cr0.15‐Co0.85Se/NF material is used as a two‐electrode device for whole water splitting, the required cell voltage is only 1.43 V to reach a current density of 10 mA cm−2, which is among the lowest values of the published catalysts up to now. In addition, the Cr0.15‐Co0.85Se/NF catalyst also exhibits excellent stability during a long period of water splitting. The experimental result demonstrates that the change of the lattice structure has an obvious influence on the electrocatalytic activity of the material. When an external electric field is applied, it facilitates the rapid electron transfer rate and enhances the electrocatalytic performance and stability of the material.
Toward Pluramycins with Epoxy Side Chain: Syntheses of Kidamycinone and Epoxykidamycinone (Saptomycinone H)
Authors: Ando Yoshio , Maezawa Yoshihiko , Shimura Jun , Kitamura Kei , Matsumoto Takashi , Suzuki Keisuke
Published: February 2020

For exploring general routes to the pluramycin‐class of antibiotics, including congeners with epoxide‐bearing side chains, syntheses of kidamycinone and its epoxide (epoxykidamycinone) have been achieved. At the stage of the A‐ring cyclization with alkene‐bearing side chain, the desired 6‐endo product was obtained as a major compound, although the corresponding undesired 5‐exo product was also formed.
Emotional Processing of Ironic Versus Literal Criticism in Autistic and Nonautistic Adults: Evidence From Eye‐Tracking
Authors: Barzy Mahsa , Filik Ruth , Williams David , Ferguson Heather J.
Published: February 2020

Typically developing adults are able to keep track of story characters' emotional states online while reading. Filik et al. showed that initially, participants expected the victim to be more hurt by ironic comments than literal, but later considered them less hurtful; ironic comments were regarded as more amusing. We examined these processes in autistic adults, since previous research has demonstrated socio‐emotional difficulties among autistic people, which may lead to problems processing irony and its related emotional processes despite an intact ability to integrate language in context. We recorded eye movements from autistic and nonautistic adults while they read narratives in which a character (the victim) was either criticized in an ironic or a literal manner by another character (the protagonist). A target sentence then either described the victim as feeling hurt/amused by the comment, or the protagonist as having intended to hurt/amused the victim by making the comment. Results from the nonautistic adults broadly replicated the key findings from Filik et al., supporting the two‐stage account. Importantly, the autistic adults did not show comparable two‐stage processing of ironic language; they did not differentiate between the emotional responses for victims or protagonists following ironic versus literal criticism. These findings suggest that autistic people experience a specific difficulty taking into account other peoples' communicative intentions (i.e., infer their mental state) to appropriately anticipate emotional responses to an ironic comment. We discuss how these difficulties might link to atypical socio‐emotional processing in autism, and the ability to maintain successful real‐life social interactions. Autism Res 2020, 13: 563–578. © 2020 International Society for Autism Research, Wiley Periodicals, Inc.

Lay Summary

In line with research showing that autistic people have difficulties considering others' mental states, we found autistic adults were impaired at distinguishing the emotions and intentions experienced by story characters who received sarcastic comments (e.g., “That was fantastic parking” in a context where someone's parking was particularly bad). These findings highlight the difficulties that autistic people experience taking into account other peoples' intentions during communication to appropriately anticipate their emotional responses. © 2020 International Society for Autism Research, Wiley Periodicals, Inc.
Rechargeable Photoactive Zn‐Air Batteries Using NiCo2S4 as an Efficient Bifunctional Photocatalyst towards OER/ORR at the Cathode
Authors: Sarawutanukul Sangchai , Tomon Chanikarn , Duangdangchote Salatan , Phattharasupakun Nutthaphon , Sawangphruk Montree
Published: February 2020

Using free solar energy in oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) electrocatalysts to enhance the efficiency of zinc‐air batteries (ZABs) has not yet been widely investigated. Herein, we report a photoactive bifunctional catalyst of spinel‐type NiCo2S4 (NCS) urchin‐like structure with rich mesopores and direct band gap energies of ca. 1.4 and 2.4 eV. The NCS catalyst exhibits high catalytic activities for both OER (ɳ=338 mV at 10 mA cm−2) and ORR (ɳ=475 mV at E1/2), comparable to that of the state‐of‐the‐art counterparts (e. g., Pt/C for ORR, RuO2 for OER). Under light illumination, the p‐type photoactive NCS catalyst can absorb visible light, generating photogenerated holes and photoelectrons via the photoelectric effect for direct conversion of photoenergy into electric energy with increasing kinetics charge transfer process and provides ca. 10 and 18.5 % lower OER and ORR overpotentials, respectively than those under the dark condition. In addition, the as‐fabricated zinc‐air battery with the photoactive NCS as the cathode exhibits decrease in voltage gap from 0.82 to 0.60 V with an increasing round‐trip efficiency from 59.2 % to 68.8 % after exposed to visible light. The zinc‐air battery with a reversible redox reaction for the simultaneous conversion of chemical and photoenergy into electric energy could open a new pathway for the utilization of a single energy conversion and storage device.
Conditional survival after neoadjuvant chemoradiotherapy and surgery for oesophageal cancer
Authors: Hagens E R C , Feenstra M L , Eshuis W J , Hulshof M C C M , van Laarhoven H W M , van Berge Henegouwen M I , Gisbertz S S
Published: February 2020

Background

Conditional survival accounts for the time already survived after surgery and may be of additional informative value. The aim was to assess conditional survival in patients with oesophageal cancer and to create a nomogram predicting the conditional probability of survival after oesophagectomy.

Methods

This retrospective study included consecutive patients with oesophageal cancer who received neoadjuvant chemoradiation followed by oesophagectomy between January 2004 and 2019. Conditional survival was defined as the probability of surviving y years after already surviving for x years. The formula used for conditional survival (CS) was: CS(x|y) = S(x + y)/S(x), where S(x) represents overall survival at x years. Cox proportional hazards models were used to evaluate predictors of overall survival. A nomogram was constructed to predict 5-year survival directly after surgery and given survival for 1, 2, 3 and 4 years after surgery.

Results

Some 660 patients were included. Median overall survival was 44·4 (95 per cent c.i. 37·0 to 51·8) months. The probability of achieving 5-year overall survival after resection increased from 45 per cent directly after surgery to 54, 65, 79 and 88 per cent given 1, 2, 3 and 4 years already survived respectively. Cardiac co-morbidity, cN category, ypT category, ypN category, chyle leakage and pulmonary complications were independent predictors of survival. The nomogram predicted 5-year survival using these predictors and number of years already survived.

Conclusion

The probability of achieving 5-year overall survival after oesophagectomy for cancer increases with each additional year survived. The proposed nomogram predicts survival in patients after oesophagectomy, taking the years already survived into account.
Prospective study of the relevance of circulating tumor cell status and neoadjuvant chemotherapy effectiveness in early breast cancer
Authors: Ni Chao , Shen Yimin , Fang Qingqing , Zhang Min , Yuan Hongjun , Zhang Jingxia , Zhong Miaochun , Zheng Yajuan
Published: February 2020

Although unequivocal evidence has shown the prognostic relevance of circulating tumor cells (CTCs) in patients with metastatic breast cancer (MBC), less evidence is available for its significance in neoadjuvant chemotherapy (NCT) in early breast cancer (BC). Here we conducted an analysis of individual data from 86 patients confirmed as invasive BC by core‐needle biopsy in Zhejiang Provincial People's Hospital between June 2013 and January 2017. The CTCs were assessed at the time after diagnosis and before surgery with the CanPatrol technique. The median follow‐up duration was 46.3 months. CTCs were detected in 37.2% of all patients (29/78) at baseline, and the presence of CTCs was associated with tumor size, tumor stage, and molecular classification. After NCT, the CTC‐positive patients were dropped from 29 to 8, and the EC‐T (epirubicin/cyclophosphamide followed by docetaxel) and TEC (docetaxel/epirubicin/cyclophosphamide) strategies reduce CTC‐positive patients from 16 to 3 and 13 to 5, respectively. The CTC‐negative conversion rates were similar in ER/PR+ HER2+ (5/7, 71.4%), ER/PR− HER2+ (8/11, 72.7%), and TNBC (7/10, 70%) during NCT. In addition, we explored the association between CTC‐negative conversion and objective response rate (partial response and complete response, ORR) and pathological complete response rate (pCR), and our results indicate that ORR was higher in patients with positive CTCs and converted to negative after NCT (ORR, P = .013; pCR, P = .0608). Our study preliminarily highlights the relevance of CTC status and NCT effectiveness in early BC using the CanPatrol system.
Kras mutation correlating with circulating regulatory T cells predicts the prognosis of advanced pancreatic cancer patients
Authors: Cheng He , Luo Guopei , Jin Kaizhou , Fan Zhiyao , Huang Qiuyi , Gong Yitao , Xu Jin , Yu Xianjun , Liu Chen
Published: February 2020

Purpose

Kras mutation and abnormal immune status are associated with pancreatic cancer development and progression. In this study, we evaluated the Kras mutation status in circulating tumor DNA and circulating T cell subsets in a cohort of advanced pancreatic cancer patients.

Methods

Samples were retrospectively obtained from a series of 210 pathological advanced pancreatic cancer patients between 2012 and 2014. The Kras mutation status was detected in cell‐free circulating tumor DNA (ctDNA) by ddPCR and circulating T cell subsets were analyzed by flow cytometry.

Results

Univariate analysis found that tumor node metastasis (TNM) stage, chemotherapy, circulating regulatory T cells, CA19‐9 levels, CA125 levels, and KrasG12D and KrasG12V mutations were significantly related to overall survival in advanced pancreatic cancer patients. Multivariate analysis identified that TNM stage (P = .03, HR:1.422), Tregs (P = .004, HR:1.522), CA19‐9 levels (P = .009, HR:1.488), KrasG12D mutation (P = .044, HR:1.353), and KrasG12V mutation (P = .001, HR:1.667) were independent prognostic markers. Furthermore, we found that KrasG12V mutation in ctDNA was correlated with high circulating proportion of Tregs, and patients with both KrasG12V mutation and high levels of Tregs were associated with extremely poor survival in advanced pancreatic cancer.

Conclusion

KrasG12V mutation was associated with high circulating regulatory T cell levels, and both of them predicted worse prognosis in advanced pancreatic cancer patients.
Characterization of the immune microenvironment in brain metastases from different solid tumors
Authors: Jiang Jinling , Wu Lihong , Yuan Fei , Ji Jun , Lin Xiaojing , Yang Wanning , Wu Junwei , Shi Min , Yang Hui , Ma Yanna , Song Xue , Zhu Zhenggang , Zhang Henghui , Zhang Jun
Published: February 2020

Background

Brain metastases are one of the most common intracranial neoplasms. Increasing evidence have indicated that systemic immunotherapy may provide long‐term benefits for brain metastases. Herein, we presented the results of an immune oncology panel RNA sequencing platform for patients with brain metastases from different primary sites.

Methods

We investigated 25 samples of human brain metastases from lung cancer (n = 12), breast cancer (n = 6), and colorectal cancer (n = 7). Besides, 13 paired samples of adjacent noncancerous brain tissue (10 from patients with lung cancer and 3 from patients with breast cancer) were collected as controls. By comparing the brain metastases and paired samples of adjacent noncancerous brain tissue from 13 patients, we detected three upregulated and six downregulated genes, representing the malignant properties of cancer cells and increased immune infiltration in the microenvironment. Next, we profiled the immune‐related genes in brain metastases from three primary cancer types.

Results

A group of genes were significantly overexpressed in the microenvironment of brain metastases from lung cancer, covering the checkpoint pathways, lymphocyte infiltration, and TCR‐coexpression. Especially, immune checkpoint molecules, PD‐L1, PD‐L2, and IDO1 were expressed at higher levels in brain metastases from lung cancer than those from the other two cancer types.

Conclusions

This study presents an immune landscape of brain metastases from different cancer types. With high RNA expression levels of PD‐1/PD‐L1 axis and immune infiltration in brain metastases, it would be worthwhile to explore the efficacy of immune checkpoint blockade for lung cancer patients with intracranial metastases.
Highly Efficient Binuclear Copper‐catalyzed Oxidation of N,N‐Dimethylanilines with O2
Authors: Liu Yuxia , Yan Yonggang , Xue Dong , Wang Zhongfu , Xiao Jianliang , Wang Chao
Published: February 2020

A binuclear copper‐salicylate complex, [Cu(Sal)2(NCMe)]2 (Sal=salicylate), was found to be an active catalyst for the oxidation of N,N‐dimethylanilines by O2, affording the corresponding N‐methyl‐N‐phenylformamides as major products. The reactions were carried out with a O2 balloon and the S/C (substrate/catalyst ratio) of the model reaction could be up to 1×105, providing a practical and highly efficient catalytic protocol for accessing N‐methyl‐N‐phenylformamides.
Flowsheet Modeling and Simulation of Biomass Steam Gasification for Hydrogen Production
Authors: Inayat Abrar , Raza Mohsin , Khan Zakir , Ghenai Chaouki , Aslam Muhammad , Shahbaz Muhammad , Ayoub Muhammad
Published: February 2020

Hydrogen production from biomass steam gasification is systematically reviewed. Equilibrium modeling and simulation studies using various techniques for effective hydrogen production are presented. Heat integration, economic analysis of the hydrogen production, and systematic design algorithms research publications are overviewed and discussed for energy‐efficient and economic hydrogen production from various biomass feedstocks. Comparison and analysis of the results strongly suggest the viable potential of biomass steam gasification for hydrogen production from small to large scales with applications for thermal heat, power generation, and many other industrial fields.
Bimetallic Ru‐Fe Nanoparticles Supported on Carbon Nanotubes for Ammonia Decomposition and Synthesis
Authors: Chen Cai , Chen Yiwen , Ali Arshid M. , Luo Wenjia , Wen Jie , Zhang Lianhong , Zhang Hui
Published: February 2020

Alloy catalysts can achieve superior performance to single metal while reducing the cost by fine‐tuning the composition and morphology. Bimetallic Ru‐Fe nanoparticles were synthesized via liquid‐phase reduction method followed by impregnation with multiwall carbon nanotubes (CNTs) to prepare Ru‐Fe/CNTs catalysts. The Ru3Fe/CNTs catalyst yields a superior catalytic stability for ammonia decomposition compared to the Ru/CNTs catalyst. Hence, the ammonia synthesis rate of the Ru3Fe/CNTs catalyst was significantly higher than that of Ru/CNTs catalyst. The potential of bimetallic catalysts with reasonable composition and proportion will expand the research of efficient catalysts for ammonia decomposition and synthesis.
Zeotype SAPO‐34 Synthesized by Combination of Templates for the Gasification of Biomass
Authors: Doan Tuan , Nguyen Khang , Dam Phong , Pham Nga , Vu Quan , Vuong Thanh Huyen , Pham Thanh Huyen , Le Minh Thang
Published: February 2020

SAPO‐34 is a crystalline microporous material, the characteristics of which are greatly influenced by synthetic parameters, especially the silica precursors and templates. In this study, the combination of templates and silica sources was optimized to obtain SAPO‐34 phases in the purest form. The physicochemical properties of the thus‐synthesized catalysts were characterized, and the Si environment in the SAPO‐34 framework was analyzed. The catalytic performance in biomass gasification was investigated in a fixed‐bed flow reactor. SAPO‐34 synthesized with triethylamine/morpholine/tetraethylammonium hydroxide templates exhibited the highest total acidity, the smallest particle size, and high surface area, and produced a large amount of light hydrocarbons in biomass gasification.
Recent Advances in Electrochemical Synthesis of Ammonia through Nitrogen Reduction under Ambient Conditions
Authors: Wang Jia , Chen Silong , Li Zijian , Li Guangkai , Liu Xien
Published: February 2020

Ammonia is an important chemical raw material, widely used in industry and agriculture, as well as an important energy storage intermediate and carbon‐free energy carrier. But, its production is limited to the traditional Haber‐Bosch process. Recently, electrochemical reduction of N2 has been attracting more and more attention, owing to the lower energy consumption and because it is environmentally friendly. However, there are a lot of problems that remain to be solved, and the main challenges are the low selectivity and catalytic activity when using this process. In this Review, we first summarize the recent development of electrocatalysts for electrochemical N2 reduction and elaborate on the reaction mechanisms of the nitrogen reduction reaction (NRR). In addition, the effects of different types of electrolyte on the NRR activity and electrolyte choice are discussed. Finally, the perspectives of electrochemical nitrogen reduction for conversion to ammonia are discussed.
New insight about the relationship between the main characteristics of precursor materials and activated carbon properties using multivariate analysis
Authors: Santos Mateus Pereira F. , da Silva Josiane F. , da Costa Ilhéu Fontan Rafael , Bonomo Renata C. F. , Santos Leandro S. , Veloso Cristiane M.
Published: February 2020

Agro‐industrial wastes are used as carbon precursors in the production of activated carbon because they are rich in lignocellulosic materials. This study aimed to investigate the relationship between the main characteristics of precursor materials and activated carbons by multivariate analysis. After characterization of the precursor materials and their respective carbons, the principal component analysis and canonical correlation analysis were performed. Materials with cellulose/lignin ratio > 3.0 led to the production of carbons with a higher pore diameter, while materials with a cellulose/lignin ratio ≤ 1.0 led to a low pore volume. Using the mathematical models obtained, it is possible to predict the carbon characteristics using only the composition data of the lignocellulosic materials.
Reinforcement of Self‐Healing Polyacrylic Acid Hydrogel with Acrylamide Modified Microcrystalline Cellulose†
Authors: Bai Changzhuang , Huang Qiuhua , Xiong Xiaopeng
Published: February 2020

Summary of main observation and conclusion

Self‐healing hydrogel such as polyacrylic acid (PAA) hydrogel has attracted increasing attention based on its promising potential applications. However, it usually suffers from low strength especially as mechanical device. Herein, a commercial microcrystalline cellulose (MCC) was modified with acrylamide to graft polyacrylamide (PAM) chains on the particle surface. The acrylamide‐modified MCC (AM‐MCC) was then dispersed in monomer solution of acrylic acid to prepare composite hydrogel. The mechanical properties of the obtained composite hydrogels and the self‐healed hydrogels were carefully measured by compressive and tensile tests, and by dynamic mechanical analysis. Our results demonstrate that introduction of a small amount of AM‐MCC such as 3 wt% can not only reinforce the original hydrogel and the healed hydrogel markedly, but also improve self‐healing efficiency obviously. The analyses indicate that in addition to the reversible multi‐interactions such as hydrogen bonding and ionic interactions, the entanglements between the PAA chains of the hydrogel matrix and the PAM chains grafted on the MCC particles have also played an important role on the improvement in mechanical performances and the healing ability of the hydrogel. Moreover, the responsiveness to exterior ion has been tested to indicate potential application of the composite hydrogel as self‐healable sensor.
Morpholine As a Scaffold in Medicinal Chemistry: An Update on Synthetic Strategies
Authors: Tzara Ariadni , Xanthopoulos Dimitrios , Kourounakis Angeliki P.
Published: February 2020

Morpholine is a frequently used heterocycle in medicinal chemistry and a privileged structural component of bioactive molecules. This is mainly due to its contribution to a plethora of biological activities as well as to an improved pharmacokinetic profile of such bioactive molecules. The synthesis of morpholines is a subject of much study due to their biological and pharmacological importance, with the last such review being published in 2013. Here, an overview of the main approaches toward morpholine synthesis or functionalization is presented, emphasizing on novel work which has not been reviewed so far. This review is an update on synthetic strategies leading to easily accessible libraries of bioactives which are of interest for drug discovery projects.