bluuebunny/crossref_metadata_2025 huggingface dataset:
Electronic Effect‐Guided Rational Design of Candida antarctica Lipase B for Kinetic Resolution Towards Diarylmethanols
Authors: Li Dan‐Yang , Lou Yu‐Jiao , Xu Jian , Chen Xiao‐Yang , Lin Xian‐Fu , Wu Qi
Published: January 2021

Herein, we developed an electronic effect‐guided rational design strategy to enhance the enantioselectivity of Candida antarctica lipase B (CALB) mutants towards bulky pyridyl(phenyl)methanols. Compared to W104A mutant previously reported with reversed S‐stereoselectivity toward sec‐alcohols, three mutants (W104C, W104S and W104T) displayed significant improvement of S‐enantioselectivity in the kinetic resolution (KR) of various phenyl pyridyl methyl acetates due to the increased electronic effects between pyridyl and polar residues. The electronic effects were also observed when mutating other residues surrounding the stereospecificity pocket of CALB, such as T42A, S47A, A281S or A281C, and can be used to manipulate the stereoselectivity. A series of bulky pyridyl(phenyl) methanols, including S‐(4‐chlorophenyl)(pyridin‐2‐yl) methanol (S‐CPMA), the intermediate of bepotastine, were obtained in good yields and ee values.

magnified image
Electrochemical Thiolation and Borylation of Arylazo Sulfones with Thiols and B2pin2
Authors: Wang Rongkang , Chen Fangming , Jiang Lvqi , Yi Wenbin
Published: January 2021

An efficient electrochemical synthesis approach of various unsymmetrical thioethers and arylboronates has been developed. Bench stable arylazo sulfones were used as radical precursors for carbon‐heteroatom bond formation under electrochemical conditions. Moreover, the scalability of this approach was evaluated by performing the electrochemical thiolation and borylation of arylazo sulfones with thiols and B2pin2 on a gram scale. This protocol not only avoided the use of stoichiometric oxidants, metal catalysts, activating agents and even added bases, but also exhibited favorable functional group tolerance.

magnified image
Tuning Nanosiliceous Framework for Enhanced Cancer Theranostic Applications
Authors: Ni Nengyi , Su Yaoquan , Wei Yuchun , Ma Yanling , Zhao Lingzhi , Sun Xiao
Published: January 2021

As nanotechnology rapidly advances, siliceous nanomaterials have become increasingly examined for biomedical applications. To further expand their advantageous physicochemical properties and counter intrinsic limitations challenging their progress toward clinical translation, strategies ranging from new fabrication methods to diverse forms of modifications have been proposed. Among them, direct incorporation of foreign species into the siliceous frameworks has emerged. The incorporation of inorganic or organic moieties into an otherwise purely siliceous framework enriches the structure with novel or improved properties. In this review, the progress of inorganic modification is mainly examined on mesoporous silica nanoparticles (MSNs) due to their widely appreciated attributes that garnered them an important position within cancer nanomedicine, while organic modifications are studied through designs of mesoporous organosilica nanoparticles (MONs). General synthesis methods and philosophies behind framework modifications are first discussed in brief. Subsequently, several interesting inorganically doped MSNs and formulations of MONs are studied for their advantages, including the role of catalysis after metal impregnation, improved biodegradability, novel stimuli‐responsiveness, role in bioimaging, and enhancing the outcomes of key treatment strategies. Finally, the advances are summarized, along with proposed prospects for these hybrid materials in their progress toward clinical use.
High‐Performance Semi‐Transparent Organic Photovoltaic Devices via Improving Absorbing Selectivity
Authors: Li Yaokai , He Chengliang , Zuo Lijian , Zhao Feng , Zhan Lingling , Li Xin , Xia Ruoxi , Yip Hin‐Lap , Li Chang‐Zhi , Liu Xu , Chen Hongzheng
Published: January 2021

Semi‐transparent organic photovoltaics (ST‐OPVs) are promising solar windows for building integration. Improving the light‐absorbing selectivity, that is, transmitting the visible photons while absorbing the invisible ones, is a key step toward high‐performance ST‐OPV. To achieve this goal, the optical properties of the active layer, transparent electrode, and capping layer are comprehensively tailored, and a highly efficient ST‐OPV with good absorbing selectivity is demonstrated. First, a numerical method is established to quantify the absorbing selectivity of materials and devices, based on which, an infrared absorbing non‐fullerene acceptor, that is, H3, is selected among a large pool of photo‐active materials. Second, an ultra‐smooth transparent thin Ag layer with small granule size is developed via polyethylenimine wetting, which alleviates light scattering and improves the electric properties for ST‐OPV. Finally, as guided by optical simulation, a TeO2 capping layer is deposited on top of the ultra‐thin Ag to further improve the light‐absorbing selectivity. As a result, the light utilization efficiency is significantly improved to 3.95 ± 0.02% (best ≈4.06%), with a good color rendering index of 76.85. These results make it one of the best among color‐neutral ST‐OPVs. This work stresses the importance of manipulating the light‐absorbing selectivity for high‐performance ST‐OPVs.
How Does External Pressure Shape Li Dendrites in Li Metal Batteries?
Authors: Shen Xin , Zhang Rui , Shi Peng , Chen Xiang , Zhang Qiang
Published: January 2021

High‐energy density lithium metal batteries have achieved great progress as next‐generation rechargeable cells. However, the huge gap in the switching from coin to pouch cells hinders their practical application. External pressure, as one discrepancy between coin and pouch cells, plays an important role in the performance of Li metal anodes. Herein the mechanism for the impact of external pressure on Li dendrites is revealed and quantified by a mechano‐electrochemical phase field model. Two influence approaches are outlined as: 1) Inhibiting the progress of electroplating reactions, which lower the rate performance of cells; 2) Shaping the morphology of Li dendrites to be smooth and dense but increasing the mechanical instability. Furthermore, a phase diagram of routine electrolytes (including electrolyte‐immersed separators and solid polymer electrolytes) with respect to various external pressures is established, giving rational guidance for designing pressure management systems in working batteries.
Carbon Anode Materials: A Detailed Comparison between Na‐ion and K‐ion Batteries
Authors: Zhang Lupeng , Wang Wei (Alex) , Lu Shanfu , Xiang Yan
Published: January 2021

As novel “post lithium‐ion batteries,” sodium‐ion batteries/potassium‐ion batteries (SIBs/PIBs) are emerging and show bright prospect in large‐scale energy storage applications due to abundant Na/K resources. Further benefits of this technology include, its low cost, chemical inertness and safety. Extensive research findings have demonstrated that carbon‐based materials are promising candidates for both SIBs and PIBs. Although the two alkali‐ion batteries have similar internal components and electrochemical reaction mechanisms, in carbon‐based materials the storage/release behaviors of Na+ and K+ are not exactly the same. Therefore, a comprehensive comparison of Na+/K+ storage behaviors in carbon anode materials is lacking. It is absolutely imperative to understand these mechanisms more clearly to achieve ideal performance. Herein, three potential Na+/K+ storage/release behaviors are discussed, which are i) intercalation/deintercalation mechanism, ii) adsorption/desorption mechanism, and iii) pore‐filling mechanism. This review not only attempts to summarize the development status of carbon anode materials (graphite, graphene, hard carbon and soft carbon), but also provides a comprehensive comparison (mechanism, capacity, rate capability, diffusion coefficient, cyclability, potassiation/sodiation potential) between SIBs and PIBs. Finally, critical issues and perspectives are discussed to demonstrate possible development directions for carbon anode materials for SIBs and PIBs.
Sustainable Batteries—Quo Vadis?
Authors: Titirici Maria‐Magdalena
Published: January 2021

Over the past 20 years, a revolution has been seen in battery research culminating with a much‐awaited Nobel Prize in Chemistry in 2019 for the development of Li‐ion batteries. New Li‐ion battery materials have been developed recently with improvements in performance. New Li battery chemistries have also emerged, exhibiting high energy density such as Li‐S, Li‐O2, Li‐metal with solid state electrolytes as well as zero‐excess Li anode metal batteries. This is tremendous progress and batteries are becoming more efficient and cheaper each year. Yet, most research in batteries is entirely focused on performance while the sustainability of all battery components making up the cell, as well as the battery chemistry itself are much overlooked. In this essay some perspectives are discussed and opinion is provided on the advancement of sustainability in battery research.
Genomic characteristics and prognostic significance of co‐mutatedASXL1/SRSF2acute myeloid leukemia
Authors: Richardson Daniel R. , Swoboda David M. , Moore Dominic T. , Johnson Steven M. , Chan Onyee , Galeotti Jonathan , Esparza Sonia , Hussaini Mohammad O. , Van Deventer Hendrick , Foster Matthew C. , Coombs Catherine C. , Montgomery Nathan D. , Sallman David A. , Zeidner Joshua F.
Published: January 2021

TheASXL1andSRSF2mutations in AML are frequently found in patients with preexisting myeloid malignancies and are individually associated with poor outcomes. In this multi‐institutional retrospective analysis, we assessed the genetic features and clinical outcomes of 43 patients withASXL1mutSRSF2mutAML and compared outcomes to patients with eitherASXL1(n = 57) orSRSF2(n = 70) mutations. Twenty‐six (60%) had secondary‐AML (s‐AML). Variant allele fractions suggested thatSRSF2mutations precededASXL1mutational events. Median overall survival (OS) was 7.0 months (95% CI:3.8,15.3) and was significantly longer in patients with de novo vs s‐AML (15.3 vs 6.4 months, respectively;P= .04 on adjusted analysis). Compared toASXL1mutSRSF2wtandASXL1wtSRSF2mut, co‐mutated patients had a 1.4 and 1.6 times increase in the probability of death, respectively (P= .049), with a trend towards inferior OS (median OS = 7.0 vs 11.5 vs 10.9 months, respectively;P= .10). Multivariable analysis suggests this difference in OS is attributable to the high proportion of s‐AML patients in the co‐mutated cohort (60% vs 32% and 23%, respectively). Although this study is limited by the retrospective data collection and the relatively small sample size, these data suggest thatASXL1mutSRSF2mutAML is a distinct subgroup of AML frequently associated with s‐AML and differs fromASXL1mutSRSF2wt/ASXL1wtSRSF2mutwith respect to etiology and leukemogenesis.
Genetic skin disorders: The value of a multidisciplinary clinic
Authors: Parker James Clayton , Rangu Sneha , Grand Katheryn Lynn , Bhoj Elizabeth Joyce , Castelo‐Soccio Leslie , Sheppard Sarah E.
Published: January 2021

Genodermatoses are inherited disorders with skin manifestations and can present with multisystem involvement, resulting in challenges in diagnosis and treatment. To address this, the expertise of dermatology and clinical genetics through a multidisciplinary clinic (Genodermatoses Clinic) were combined. A retrospective cohort study of 45 children seen between March 2018 and February 2019 in the Genodermatoses Clinic at The Children's Hospital of Philadelphia was performed. Patient demographics, referral information, genetic testing modality, diagnoses, and patient satisfaction scores were evaluated to assess the clinic's impact. The majority of patients (42.2%) were referred from Dermatology and 86.7% were referred for diagnosis. Two‐thirds of the patients were recommended genetic testing, and subsequently 73.3% completed testing. Nearly three‐quarters, 26 out of 36 patients (72.2%), of our undiagnosed patients received a clinical and/or molecular diagnosis, which is imperative in managing their care. Twenty‐two individuals pursued genetic testing. In eight individuals (36%), molecular testing was diagnostic. However, in two individuals the molecular diagnosis did not completely explain the phenotype. However, there are still obstacles to genetic testing, such as cost of testing and insurance barriers. Almost all (91.4%) rated the Genodermatoses Clinic as “Very Good,” the top Press Ganey score. High patient satisfaction scores suggest a positive impact of the Genodermatoses clinic, emphasizing the importance to increase support for the clinical and administrative time needed for patients with genodermatoses.
Recent Advances in the Synthesis of CF3‐ or HCF2‐Substituted Cyclopropanes
Authors: Wu Wen‐Feng , Lin Jin‐Hong , Xiao Ji‐Chang , Cao Yu‐Cai , Ma Yanfang
Published: January 2021

CF3‐ or HCF2‐substituted cyclopropanes are of great interest in pharmaceutical chemistry and agrochemistry, and thus significant efforts have been directed towards the development of efficient methods for the installation of these motifs. This Minireview summarizes recent efforts for the construction of CF3‐ or HCF2‐substituted cyclopropanes. CF3‐cyclopropanes are usually synthesized by a transition‐metal‐catalyzed cyclopropanation of alkenes with a trifluoromethylcarbene generated in situ from a diazocompound, CF3CHN2 or CF3C(Ar)N2. The synthesis of HCF2‐cyclopropanes remains largely unexplored. Some difluoromethylcarbene reagents have been developed, such as HCF2CHN2, Ph2S+CH2CF2H TfO−, and difluoroacetaldehyde N‐triftosylhydrazone (DFHZ‐Tfs), and cyclopropanation of alkenes with these reagents could also occur by transition metal catalysis. These protocols may find great utility in the synthesis of biologically active molecules.
C3h‐symmetric and Cs‐symmetric Triformyl Triindolo‐Truxenes: Synthesis and Properties
Authors: Chen Jun‐Bo , Lu Ru‐Qiang , Wang Xin‐Chang , Qu Hang , Liu Hao‐Liang , Zhang Hui , Cao Xiao‐Yu
Published: January 2021

C3h‐symmetric and Cs‐symmetric triformyl triindolo‐truxenes with different substitution positions of formyl groups were developed by two synthetic strategies. Direct formylation of triindolo‐truxene using Rieche formylation produced C3h‐symmetric and Cs‐symmetric triformyl triindolo‐truxenes in one‐pot. Four‐step synthesis starting from truxene gave a carbonyl‐modified C3h‐symmetric triformyl triindolo‐truxene. The optical and electrochemical properties of triformyl triindolo‐truxenes were modulated by changing the substitution positions of formyl groups and introducing carbonyl groups into molecules. The Cs‐symmetric triformyl triindolo‐truxenes exhibited red‐shifted absorption and emission, higher HOMO levels, and narrower HOMO‐LUMO gaps than those of C3h‐symmetric analogues. Furthermore, carbonyl‐modified C3h‐symmetric triformyl triindolo‐truxene showed the longest absorption and emission and narrowest HOMO‐LUMO gap among its analogues. The assembly of triformyl triindolo‐truxenes in single crystals and solution was investigated. This work provides valuable building blocks for constructing supramolecular architectures and adds new aspects of reactivity and structure‐property relationship of triindolo‐truxene.
FeCl2‐Catalyzed Direct C2‐Benzylation of Benzofurans with Diarylmethanes via Cross Dehydrogenative Coupling
Authors: Zhou Jiacheng , Li Tianci , Li Meichao , Li Chunmei , Hu Xinquan , Jin Liqun , Sun Nan , Hu Baoxiang , Shen Zhenlu
Published: January 2021

A direct strategy for the iron‐catalyzed oxidative coupling C2‐functionalization of benzofurans with unactivated diarylmethanes has been established. The developed procedure provides a straightforward access to C2‐benzylation of benzofurans from simple and abundant starting materials without the need for pre‐functionalization or specific substituted functional groups of both, substrates and coupling partners.
Non‐oxidative Coupling of Methane: N‐type Doping of Niobium Single Atoms in TiO2–SiO2 Induces Electron Localization
Authors: Chen Ziyu , Wu Shiqun , Ma Jiayu , Mine Shinya , Toyao Takashi , Matsuoka Masaya , Wang Lingzhi , Zhang Jinlong
Published: January 2021

Photodriven nonoxidative coupling of CH4 (NOCM) is an attractive potential way to use abundant methane resources. Herein, an n‐type doped photocatalyst for NOCM is created by doping single‐atom Nb into hierarchical porous TiO2–SiO2 (TS) microarray, which exhibits a high conversion rate of 3.57 μmol g−1 h−1 with good recyclability. The Nb dopant replaces the 6‐coordinated titanium on the (1 0 1) plane and forms shallow electron‐trapped surface polarons along [0 1 0] direction and the comparison of different models proves that the electron localization caused by the n‐type doping is beneficial to both methane activation and ethane desorption. The positive effect of n‐type dopant on CH4 conversion is further verified on Mo‐, W‐ and Ta‐doped composites. In contrast, the doping of p‐type dopant (Ga, Cu, Fe) shows a less active influence.
Coassemblierung von Helices auf Makroebene durch chiralitätstransferierende, temperaturresponsive, Kohlenhydrat‐basierte Bolaamphiphile und 1,4‐Phenylenbisboronsäure
Authors: Wang Shuang , Forster Marcel C. , Xue Kai , Ehlers Florian , Pang Bo , Andreas Loren B. , Vana Philipp , Zhang Kai
Published: January 2021

Wir zeigen das erste Beispiel von Helices, die durch temperaturresponsive, Kohlenhydrat‐basierte Bolaamphiphile (CHO‐Bolas) und 1,4‐Phenylenbisboronsäure (BDBA) auf der Makroskala coassembliert wurden. Die CHO‐Bolas enthielten hydrophile Glucose‐ oder Mannose‐Einheiten und ein hydrophobes Cumarin‐Dimer. Sie zeigten in wässriger Lösung einen reversiblen, temperaturresponsiven Mizellen‐zu‐Vesikel‐Übergang (MVT). Nach dem Binden der Kohlenhydrat‐Einheiten mit den Boronsäure‐Gruppen des BDBA in alkalischer Lösung wurden rechtshändige Helices über einen temperaturgetriebenen Chiralitätstransfer der d‐Glucose oder d‐Mannose von der molekularen auf die supramolekularen Ebene gebildet. Diese Helices wurden durch nicht umgesetztes BDBA, aus CHO‐Bolas und BDBA gebildete Boronsäureester (B‐O‐C‐Bindungen) sowie Boroxinanhydride (B‐O‐B) aus der Selbstkondensation von BDBA coassembliert. Nach Erhitzen bei 300 °C unter Stickstoff zeigten die Helices eine exzellente morphologische Stabilität. Darüber hinaus emittierten sie helle, blaue Lumineszenz infolge von starker Selbstkondensation des BDBA und Zerfall des Cumarin‐Dimers.
Fine‐Tuning the Spring‐Like Motion of an Anion‐Based Triple Helicate by Tetraalkylammonium Guests
Authors: Liang Lin , Li Boyang , Zhang Wenyao , Li Anyang , Zheng Bo , Yang Xiao‐Juan , Wu Biao
Published: January 2021

Supramolecular springs are a class of molecular devices that may provide implications to the macroscopic spring behavior from the molecular level. Helical structures are suitable molecular springs because the specific twisting of the helical strands can cause spring‐like (extension‐contraction) movement along the axis upon external stimuli. Herein we report an anion‐based triple‐helicate spring, which can undergo reversible contraction–extension motion through introduction and removal of tetraalkylammonium cations, including TMA+ and analogous irregular tetrahedral cations bearing different alkyl chains, while the relative orientation of the two phosphate ions changes to facilitate guest inclusion. Notably, the degree of contraction (shortening of the helical pitch) can be fine‐tuned by varying the shape and size of guest cation. However, with the larger cations (TEA+, TPA+ and TBA+), the meso‐helicate configuration is obtained, which interconverts with the helicate by addition/removal of TMA+ ion.
Rechargeable K‐CO2 Batteries with a KSn Anode and a Carboxyl‐Containing Carbon Nanotube Cathode Catalyst
Authors: Lu Yong , Cai Yichao , Zhang Qiu , Ni Youxuan , Zhang Kai , Chen Jun
Published: January 2021

Metal K‐CO2 batteries suffer from large polarization and safety hazards, which mainly result from the difficult decomposition of K2CO3 and dendrite growth. Moreover, the battery redox mechanism remains not fully understood. Here we report K‐CO2 batteries with KSn alloy as the anode and carboxyl‐containing multi‐walled carbon nanotubes (MWCNTs‐COOH) as the cathode catalyst, proving the redox mechanism to be 4 KSn + 3 CO2 ⇄ 2 K2CO3 + C + 4 Sn. Compared with K metal, the less active and dendrite‐free KSn anode effectively enhances the safety and stability of CO2 batteries. More importantly, the strong electrostatic interaction between MWCNTs‐COOH and K2CO3 weakens the C=O bond in K2CO3 and thus facilitates K2CO3 decomposition. As a result, the K‐CO2 batteries show excellent cycling stability (an overpotential increase of 0.89 V after 400 cycles) and good rate performance (up to 2000 mA g−1). This work paves a way to develop highly stable and safe CO2‐based batteries.
Macroscalar Helices Co‐Assembled from Chirality‐Transferring Temperature‐Responsive Carbohydrate‐Based Bolaamphiphiles and 1,4‐Benzenediboronic Acid
Authors: Wang Shuang , Forster Marcel C. , Xue Kai , Ehlers Florian , Pang Bo , Andreas Loren B. , Vana Philipp , Zhang Kai
Published: January 2021

We present the first example of macroscalar helices co‐assembled from temperature‐responsive carbohydrate‐based bolaamphiphiles (CHO‐Bolas) and 1,4‐benzenediboronic acid (BDBA). The CHO‐Bolas contained hydrophilic glucose or mannose moieties and a hydrophobic coumarin dimer. They showed temperature‐responsive reversible micelle‐to‐vesicle transition (MVT) in aqueous solutions. After the binding of carbohydrate moieties with boronic acids of BDBA in their alkaline solutions, right‐handed helices were formed via the temperature‐driven chirality transfer of d‐glucose or d‐mannose from the molecular to supramolecular level. These helices were co‐assembled by unreacted BDBA, boronate esters (B−O−C bonds) between CHO‐Bolas and BDBA, as well as boroxine anhydrides (B−O−B bonds) of self‐condensed BDBA. After heating at 300 °C under nitrogen, the helices displayed excellent morphological stability. Moreover, they emitted bright blue luminescence caused by strong self‐condensation of BDBA and decomposition of coumarin dimers.
Nanostructured rigid polyurethane foams with improved specific thermo‐mechanical properties using bacterial nanocellulose as a hard segment
Authors: Benavides Sofía , Armanasco Franco , Cerrutti Patricia , Chiacchiarelli Leonel Matías
Published: January 2021

Rigid polyurethane foams (RPUFs) were synthesized with bacterial nanocellulose (BNC) at concentrations of up to 0.5 wt% using two insertion routes based on its reaction with the isocyanate precursor (ISO route) and the formation of a colloidal dispersion in the polyol precursor (POL route). The results indicated that, for BNC concentrations of only 0.1 wt%, drastic improvements of the specific elastic compressive modulus (+244.2%) and strength (+77.5%) were measured for foams with apparent density of 46.4+/− 4.7 Kg.m−3. The chemical reaction of BNC with the precursor was corroborated through the measurement of the isocyanate number and FTIR analysis. The BNC caused a significant nucleation effect, decreasing the cell size up to 39.7%. Differential scanning calorimetry analysis revealed that the BNC had a strong effect on post‐cure enthalpy, particularly for the POL route. Dynamical mechanical thermal analysis under flexural conditions proved that, regardless of BNC concentration, the incorporation of BNC caused anisotropy and that the ISO route contributed to an enhanced damping factor at high temperatures. These results prove that the ISO route is a key aspect to achieve foamed nanocomposites with improved specific mechanical properties.
Dielectric performance of composites of BaTiO3 and polymers for capacitor applications under microwave frequency
Authors: Basturk S. Bahar , Dancer Claire E. J. , McNally Tony
Published: January 2021

Composites of nano‐sized barium titanate (BaTiO3) with volume fractions up to 0.5 and poly(butylene terephthalate) (PBT) or linear low‐density polyethylene (LLDPE) were made via extrusion. Scanning electron microscopy demonstrated that BaTiO3 is well dispersed in the polymer matrices. The crystalline content (DSC) and thermal stability (TGA) of both polymers decreased with increasing BaTiO3 loading. Dielectric properties of the composites were measured using a vector network analyzer. Both dielectric permittivity and tangent loss increased with increasing BaTiO3 content. At 2.45 GHz, the dielectric permittivity for 48 vol% BaTiO3‐filled LLDPE and 43 vol% BaTiO3‐filled PBT was 25 and 21.2, respectively. There was a good fit between the Lichtenecker model and experimental data obtained up to a certain value, with the permittivity variations being dependent on volume fraction. The improved dielectric performance achieved on inclusion of BaTiO3 confirms both composite systems as potential candidates for microwave frequency capacitor applications.
Geophysical survey at the early Christian complex of Son Peretó (Mallorca, Balearic Islands, Spain)
Authors: Mas Florit Catalina , Cau Ontiveros Miguel Ángel , Meyer Cornelius , Sala Roger , Ortiz Helena , RodrÍguez Simón Pedro
Published: January 2021

Rural basilicas are the most important evidence of Christianization of the countryside on the island of Mallorca (Balearic Islands, Spain). Recent investigations of rural landscape transformations suggest that some churches were built along communication routes and linked to preexisting settlements. To obtain new data that could support this hypothesis, a geophysical survey has been carried out at the early Christian complex of Son Peretó, one of the most emblematic sites for the understanding of Late Antiquity on the island. The objective was to better define the site investigating the possible presence of other remains related to the Christian complex, that is undergoing excavation, or to a previous settlement that was later Christianized. The geophysical survey was carried out combining magnetometry and ground‐penetrating radar. For the magnetic investigation, a multiprobe gradiometer array was used. GPR was used to examine the areas nearby the remains already excavated and to better define areas where the magnetic data revealed interesting anomalies. GPR data were collected using an IDS GPR system. The results revealed both the presence of architectural remains beneath the soil that help define the Early Christian complex, as well as other remains that suggest the church was part of a larger settlement.
How online review richness impacts sales: An attribute substitution perspective
Authors: Yin Hang , Zheng Shuang , Yeoh William , Ren Jie
Published: January 2021

Richer forms of online reviews such as videos or follow‐on reviews convey ‘additional information and can attract consumers’ attention. However, prior studies focused mostly on the relationship between aggregated online reviews and sales. This paper investigates the impact of online review richness (i.e., reviews containing videos or follow‐on reviews) on sales. Leveraging attribute substitution theory, we conjecture that online review richness can provide heuristic cues in the online shopping environment to help consumers make better purchase decisions. Using data from JD.com, we found that reviews containing either videos or follow‐on reviews positively affect sales. In addition, different product types can also serve as heuristic cues to replace target cues, which can further affect how different forms of online review richness affect sales. We found that the impact of online review richness on sales is stronger for utilitarian products than for hedonic products, and stronger for negatively commented products than for positively commented products. Moreover, we conducted two online experiments and confirmed that the causal relationship is from online review richness to sales. The research findings offer practical implications for online retailers and constitute one of the first steps toward a better understanding of the relationship between online review richness and sales.
Rigorous derivation of dark energy and inflation as geometry effects in Covariant Canonical Gauge Gravity
Authors: Vasak David , Kirsch Johannes , Struckmeier Jürgen
Published: January 2021

The cosmological implications of the Covariant Canonical Gauge Theory of Gravity (CCGG) are investigated. CCGG is a Palatini theory derived from first principles using the canonical transformation formalism in the covariant Hamiltonian formulation. The Einstein‐Hilbert theory is thereby extended by a quadratic Riemann‐Cartan term in the Lagrangian. Moreover, the requirement of covariant conservation of the stress‐energy tensor leads to necessary presence of torsion. In the Friedman universe that promotes the cosmological constant to a time‐dependent function, and gives rise to a geometrical correction with the EOS of dark radiation. The resulting cosmology, compatible with the ΛCDM parameter set, encompasses bounce and bang scenarios with graceful exits into the late dark energy era. Testing those scenarios against low‐z observations shows that CCGG is a viable theory.
Icaritin and icariin reduce p‐Tau levels in a cell model of Alzheimer's disease by downregulating glycogen synthase kinase 3β
Authors: Li Ying , Dai Shirui , Huang Nanqu , Wu Jie , Yu Changyin , Luo Yong
Published: January 2021

This study aimed to explore the neuroprotective effect of icariin/icaritin (ICA/ICT) and the role of ICA/ICT in the treatment of Alzheimer's disease (AD). ICA and ICT were used to treat okadaic acid (OA)‐induced Tau hyperphosphorylation in SH‐SY5Y cells. We detected the relative changes in Tau, p‐Tau, protein phosphatase 2A (PP2A), and glycogen synthase kinase 3β (GSK‐3β) by Western blotting and enzyme‐linked immunosorbent assay. At 40 nmol/L OA, the cell viability of the SH‐SY5Y cells was significantly changed. We used different concentrations of ICA and IC to treat AD model cells and found that the effect of 2.5 μmol/L ICA and 1 μmol/L ICT was best after 48 H of treatment. After SH‐SY5Y cell induction, the p‐Tau levels were increased (P < 0.05); after the ICA/ICT treatment, the p‐Tau and GSK‐3β levels were decreased (P < 0.05), although PP2A expression did not change (P > 0.05). We found that ICA and ICT exert an effect on AD model cells by decreasing the levels of GSK‐3β and p‐Tau. The therapeutic effect of ICT is slightly better than that of ICA. Although these drugs were effective in the cell model, more studies are required to determine whether they are promising for the treatment and prevention of AD.
Use of 5‐Thio‐L‐Fucose to modulate binding affinity of therapeutic proteins
Authors: Zimmermann Martina , Nguyen Melanie , Schultheiss Christian M. , Kolmar Harald , Zimmer Aline
Published: January 2021

The reduction of antibody core‐fucosylation is known to enhance antibody‐dependent cellular cytotoxicity (ADCC). In this study, 5‐Thio‐l‐Fucose (ThioFuc) was investigated as a media and feed supplement for modulating the fucosylation profile of therapeutic proteins and, thereby, improving the resulting effector functions. Glycan analysis of five different therapeutic proteins produced by a diverse set of Chinese hamster ovary cell lines demonstrated a clone dependent impact of ThioFuc treatment. Using rituximab as a model, an efficient dose‐ and time‐dependent reduction of core‐fucosylation up to a minimum of 5% were obtained by ThioFuc. Besides a concomitant increase in the afucosylation level up to 48%, data also revealed up to 47% incorporation of ThioFuc in place of core‐fucosylation. In accordance with the glycan data, antibodies produced in the presence of ThioFuc revealed an enhanced FcγRIIIa binding up to 7.7‐fold. Furthermore, modified antibodies subjected to a cell‐based ADCC reporter bioassay proved to exert both a 1.5‐fold enhanced ADCC efficacy and 2.6‐fold enhancement in potency in comparison to their native counterparts—both of which contribute to an improvement in the ADCC activity. In conclusion, ThioFuc is a potent fucose derivative with potential applications in drug development processes.
Study of rapid reorganization of visual neurofunctions with the resting‐state functional MRI in pituitary adenoma patients with vision improvement after transsphenoidal surgery
Authors: Wang Fuyu , Wang Peng , Liu Yuyang , Zhou Tao , Meng Xianghui , Jiang Jinli
Published: January 2021

Introduction

To investigate changes of vision‐related resting‐state activity in pituitary adenoma (PA) patients with visual improvement after transsphenoidal surgery.

Methods

14 PA patients with visual improvement after surgery were enrolled. The resting‐state functional MRI and neuro‐ophthalmologic evaluation were performed before and after the operation. The functional connectivity (FC) of 8 seeds (the primary visual cortex (V1), the secondary visual cortex (V2), the middle temporal visual cortex (MT+), and fusiform gyrus(FG)) was evaluated. A paired t test was conducted to identify the differences between the two groups.

Results

Compared with the preoperation counterparts, the PA patients with improved vision exhibited decreased FC with the V1, V2, MT+, FG in the left paracentral lobule, bilateral lingual gyrus, precentral gyrus(BA 4), right superior temporal gyrus(BA 22), left fusiform gyrus, bilateral middle occipital gyrus (BA 19), left cuneus, right inferior occipital gyrus, left superior frontal gyrus, right cuneus, left superior parietal lobule(BA 7),the medulla, right postcentral gyrus, and increased FC in the right middle frontal gyrus, left inferior parietal lobule (BA 40), left declive, right lentiform nucleus, inferior frontal gyrus, right superior frontal gyrus(BA 11), cingulate gyrus(BA 32), right putamen, right thalamus, left medial frontal gyrus, left claustrum, left superior frontal Medial, right rectal gyrus(BA 25) and right parahippocampal gyrus.

Conclusions

The results show most subareas within the visual cortex exhibit decreased functional connectivity. The functional changes in subareas within default mode network (DMN), action observation network (AON) and the multisensory system in PAs propose that vision improvement may lead to function remodeling in higher‐order cortex.
Immediate Loading of Four Guided Unsplinted Narrow Implants Supporting a Maxillary Overdenture: A Minimally Invasive Approach
Authors: Agusto Michele , Kordusky Benjamin , Bryington Matthew S. , Salman Arif , Schincaglia Gian Pietro
Published: January 2021

Introduction

Little evidence is available on the loading protocols for implant‐supported overdentures in the treatment of the edentulous maxilla. There are only a few case‐reports available to document the feasibility of immediate loading for maxillary overdenture, and the majority of the publications include the use of splinted implants. This paper presents a case report of immediately loaded narrow diameter implants supporting a maxillary overdenture using Locator abutments.

Case Presentation

A 64‐year‐old, fully edentulous patient presented with a maxillary complete removable denture. A dual cone beam computed tomography scan was obtained, and the surgical planning was performed. Four 3.3 mm diameter implants were placed at the lateral incisor and second premolar positions, using a guided and flapless approach. Locator abutments were placed, and the denture was connected immediately. The patient was instructed not to remove the prosthesis for 1 week and to follow a soft diet regimen for 2 weeks. Clinical and radiographic evaluation showed positive results at 12 months, with neither prosthetic nor implant complications.

Conclusion

This is a proof of principle case report, which demonstrates the possibility of immediately loading four guided narrow diameter implants supporting a maxillary overdenture using a Locator retention system.
Serve your community by listening, rather than justifying actions
Authors: Sutton Halley
Published: January 2021

Kelly Nee came to Boston University after 33 years in the Boston Police Department. While with the BPD, she rose to the rank of Deputy Superintendent, and worked in a variety of different divisions, including the gang unit, sexual assault and domestic violence, investigations, and after the Boston Marathon bombing in 2014, she was moved to the Bureau of Intelligence and Analysis.
Comparative Study of Chemical Composition, Cholinesterase Inhibition and Antioxidant Potential of Mentha pulegium L. Essential Oil
Authors: Bektašević Mejra , Politeo Olivera , Carev Ivana
Published: January 2021

Perennial plant Mentha pulegium L. (pennyroyal, Lamiaceae) can be found in Europe and Mediterranean. In areas where it thrives, M. pulegium is used in nutrition and as medicinal plant. Essential oil of M. pulegium is also a frequent constituent of foods and fragrances, because of mint‐like odor. Regarding the use of M. pulegium in traditional medicine and nutrition, as well as fact that essential oils are potential sources of bioactive components, this study was conducted to examine the chemical composition of essential oil of M. pulegium wild growing in Bosnia and Herzegovina and its biological activity. The chemical profile testing was made using GC/MS and GC/FID technique. Potential of cholinesterase inhibition was tested by Ellman's assay. The antioxidant activity was tested by DPPH and FRAP assay. The dominant components in analyzed oil were pulegone 54.4 %, p‐menthone 14.0 % and piperitenone 12.8 %. Good antioxidant activity and moderate cholinesterase inhibition potential of tested essential oil indicates to possibility of its use in treatment of diseases related to free radicals, Alzheimer disease and as lipid protecting antioxidant.
Validation of common reference genes stability in exosomal mRNA‐isolated from liver and breast cancer cell lines
Authors: Gorji‐Bahri Gilar , Moradtabrizi Niloofar , Vakhshiteh Faezeh , Hashemi Atieh
Published: January 2021

Accurate relative gene expression analysis by reverse transcription‐quantitative polymerase chain reaction relies on the usage of suitable reference genes for data normalization. The RNA content of small extracellular vesicles including exosomes is growingly considered as cancer biomarkers. So, reliable relative quantification of exosomal messenger RNA (mRNA) is essential for cancer diagnosis and prognosis applications. However, suitable reference genes for accurate normalization of a target gene in exosomes derived from cancer cells are not depicted yet. Here, we analyzed the expression and stability of eight well‐known reference genes namely GAPDH, B2M, HPRT1, ACTB, YWHAZ, UBC, RNA18S, and TBP in exosomes‐isolated from the liver (Huh7, HepG2, PLC/PRF/5) and breast (SK‐BR‐3) cancer cell lines using five different algorithms including geNorm, BestKeeper, Delta Ct, NormFinder, and RefFinder. Our results showed that ACTB, TBP, and HPRT1 were not expressed in exosomes‐isolated from studied liver and breast cancer cell lines. The geNorm and BestKeeper algorithms indicated GAPDH and UBC as the most stable candidates. Moreover, Delta Ct and NormFinder algorithms showed YWHAZ as the most stable reference genes. Comprehensive ranking calculated by the RefFinder algorithm also pointed out GAPDH, YWHAZ, and UBC as the first three stable reference genes. Taken together, this study validated the common reference genes stability in exosomal mRNA derived from liver and breast cancer cell lines for the first time. We believe that this study would be the first step in finding more stable reference genes in exosomes that triggers more accurate detection of exosomal biomarkers.
Abrogation of histone deacetylases (HDACs) decreases survival of chronic myeloid leukemia cells: New insight into attenuating effects of the PI3K/c‐Myc axis on panobinostat cytotoxicity
Authors: Zehtabcheh Sara , Yousefi Amir‐Mohammad , Salari Sina , Safa Majid , Momeny Majid , Ghaffari Seyed H. , Bashash Davood
Published: January 2021

Although the identification of tyrosine kinase inhibitors (TKIs) has changed the treatment paradigm of many cancer types including chronic myeloid leukemia (CML), still adjustment of neoplastic cells to cytotoxic effects of anticancer drugs is a serious challenge. In the area of drug resistance, epigenetic alterations are at the center of attention and the present study aimed to evaluate whether blockage of epigenetics mechanisms using a pan‐histone deacetylase (HDAC) inhibitor induces cell death in CML‐derived K562 cells. We found that the abrogation of HDACs using panobinostat resulted in a reduction in survival of the K562 cell line through p27‐mediated cell cycle arrest. Noteworthy, the results of the synergistic experiments revealed that HDAC suppression could be recruited as a way to potentiate cytotoxicity of Imatinib and to enhance the therapeutic efficacy of CML. Here, we proposed for the first time that the inhibitory effect of panobinostat was overshadowed, at least partially, through the aberrant activation of the phosphoinositide 3‐kinase (PI3K)/c‐Myc axis. Meanwhile, we found that upon blockage of autophagy and the proteasome pathway, as the main axis involved in the activation of autophagy, the anti‐leukemic property of the HDAC inhibitor was potentiated. Taken together, our study suggests the beneficial application of HDAC inhibition in the treatment strategies of CML; however, further in vivo studies are needed to determine the efficacy of this inhibitor, either as a single agent or in combination with small molecule inhibitors of PI3K and/or c‐Myc in this malignancy.
Successful treatment of IgG4‐related hypertrophic pachymeningitis with induction rituximab and dexamethasone followed by maintenance rituximab
Authors: Seegobin Karan , Moustafa Muhamad A. , Gannon Nicole , Keller Katelyn , Hastings Jacquelyn , Gupta Vivek , Tun Han W. , Jiang Liuyan
Published: January 2021

IgG4‐related disease (IgG4RD) with intracranial involvement is rare. We report a 56‐year‐old male who had an excellent response to rituximab and dexamethasone after going undiagnosed for 5 years. After 3 years of rituximab maintenance, he has no evidence of disease on brain MRI.
Two new reported cases of 16q22.3q23.3 duplication syndrome highlight intrafamilial variability and potential sex expression differences within a rare duplication syndrome
Authors: Gunther Kathryn , Mowrey Kate , Farach Laura Schoch
Published: January 2021

Two new cases of 16q22.3q23.3 Duplication syndrome demonstrate that phenotype can vary from severely affected to mild psychiatric concerns, even within the same family and identical duplications.
Na6MQ4 (M=Zn, Cd; Q=S, Se): Promising New Ternary Infrared Nonlinear Optical Materials
Authors: Huang Yi , Gao Le , Yu HaoHai , Yang Zhihua , Li Junjie , Pan Shilie
Published: January 2021

Four sodium‐based ternary IR nonlinear optical (NLO) materials, Na6MQ4 (M=Zn, Cd; Q=S, Se), were prepared through a high‐temperature flux method. The crystal structure of the compounds is built up of isolated [MQ4] tetrahedra and a 3D framework formed by the NaQn (n=4, 5) units. The two selenides, Na6MSe4 (M=Zn, Cd), as promising IR NLO materials, show moderate second‐harmonic generation (SHG) responses (0.9 and 0.5×AgGaS2) with good phase‐matching behavior, as well as high laser damage thresholds (2 and 1.9×AgGaS2). The two sulfides, Na6MS4 (M=Zn, Cd), exhibit higher laser damage thresholds (13 and 4×AgGaS2), but smaller SHG responses (0.3 and 0.2×AgGaS2). Theoretical calculations and statistical analyses indicate that the SHG effect and band gap in the compounds originate mainly from the distorted NaQ4 NLO‐active units with a short Na−S bond length, which provides a new insight into the design of novel IR NLO materials.
Directed Design of a AuI Complex with a Reduced Mesoionic Carbene Radical Ligand: Insights from 1,2,3‐Triazolylidene Selenium Adducts and Extensive Electrochemical Investigations
Authors: Beerhues Julia , Neubrand Maren , Sobottka Sebastian , Neuman Nicolás I. , Aberhan Hannes , Chandra Shubhadeep , Sarkar Biprajit
Published: January 2021

Carbene‐based radicals are important for both fundamental and applied chemical research. Herein, extensive electrochemical investigations of nine different 1,2,3‐triazolylidene selenium adducts are reported. It is found that the half‐wave potentials of the first reduction of the selones correlate with their calculated LUMO levels and the LUMO levels of the corresponding triazolylidene‐based mesoionic carbenes (MICs). Furthermore, unexpected quasi‐reversibility of the reduction of two triazoline selones, exhibiting comparable reduction potentials, was discovered. Through UV/Vis/NIR and EPR spectroelectrochemical investigations supported by DFT calculations, the radical anion was unambiguously assigned to be triazoline centered. This electrochemical behavior was transferred to a triazolylidene‐type MIC‐gold phenyl complex resulting in a MIC‐radical coordinated AuI species. Apart from UV‐Vis‐NIR and EPR spectroelectrochemical investigations of the reduction, the reduced gold‐coordinated MIC radical complex was also formed in situ in the bulk through chemical reduction. This is the first report of a monodentate triazolylidene‐based MIC ligand that can be reduced to its anion radical in a metal complex. The results presented here provide design principles for stabilizing radicals based on MICs.
Regioselective Synthesis of 1,2,3,4‐Tetrasubstituted Arenes by Vicinal Functionalization of Arynes Derived from Aryl(Mes)iodonium Salts**
Authors: Nilova Aleksandra , Sibbald Paul A. , Valente Edward J. , González‐Montiel Gisela A. , Richardson H. Camille , Brown Kevin S. , Cheong Paul Ha‐Yeon , Stuart David R.
Published: January 2021

Herein, the synthesis of 1,2,3,4‐tetrasubstituted benzenoid rings, motifs found in pharmaceutical, agrochemical, and natural products, is described.[1] In the past, the regioselective syntheses of such compounds have been a significant challenge. This work reports a method using substituted arynes derived from aryl(Mes)iodonium salts to access a range of densely functionalized 1,2,3,4‐tetrasubstituted benzenoid rings. Significantly, it was found that halide substituents are compatible under these conditions, enabling post‐synthetic elaboration via palladium‐catalyzed coupling. This concise strategy is predicated on two regioselective events: 1) ortho‐ deprotonation of aryl(Mes)iodonium salts to generate a substituted aryne intermediate, and 2) regioselective trapping of said arynes, thereby improving previously reported reaction conditions to generate arynes at room temperature and in shorter reaction times. Density functional theory (DFT) computations and linear free energy relationship (LFER) analysis suggest the regioselectivity of deprotonation is influenced by both proximal and distal ring substituents on the aryne precursor. A competition experiment further reveals the role of arene substituents on relative reactivity of aryl(Mes)iodoniums as aryne precursors.
Synthesis of 3‐Methylthioindolesvia Intramolecular Cyclization of 2‐Alkynylanilines Mediated by DMSO/DMSO‐d6 and SOCl2
Authors: Li Xuemin , Zhang Beibei , Zhang Jingran , Wang Xi , Zhang Dongke , Du Yunfei , Zhao Kang
Published: January 2021

Main observation and conclusion

The intramolecular cyclization of 2‐alkynylanilines mediated by DMSO/SOCl2 was found to afford biologically interesting 3‐methylthioindoles, which are rarely obtained by the exiting methods. DMSO could also be replaced with its deuterated counterpart, enabling the method applicable to the construction of indole skeleton bearing a SCD3 moiety at its 3‐position.