bluuebunny/crossref_metadata_2025_split huggingface dataset:
Impact of Side‐Chain Hydrophilicity on Packing, Swelling, and Ion Interactions in Oxy‐Bithiophene Semiconductors
Authors: Siemons Nicholas , Pearce Drew , Cendra Camila , Yu Hang , Tuladhar Sachetan M. , Hallani Rawad K. , Sheelamanthula Rajendar , LeCroy Garrett S. , Siemons Lucas , White Andrew J. P. , McCulloch Iain , Salleo Alberto , Frost Jarvist M. , Giovannitti Alexander , Nelson Jenny 
Published: August 2022

AbstractExchanging hydrophobic alkyl‐based side chains to hydrophilic glycol‐based side chains is a widely adopted method for improving mixed‐transport device performance, despite the impact on solid‐state packing and polymer‐electrolyte interactions being poorly understood. Presented here is a molecular dynamics (MD) force field for modeling alkoxylated and glycolated polythiophenes. The force field is validated against known packing motifs for their monomer crystals. MD simulations, coupled with X‐ray diffraction (XRD), show that alkoxylated polythiophenes will pack with a “tilted stack” and straight interdigitating side chains, whilst their glycolated counterpart will pack with a “deflected stack” and an s‐bend side‐chain configuration. MD simulations reveal water penetration pathways into the alkoxylated and glycolated crystals—through the π‐stack and through the lamellar stack respectively. Finally, the two distinct ways triethylene glycol polymers can bind to cations are revealed, showing the formation of a metastable single bound state, or an energetically deep double bound state, both with a strong side‐chain length dependence. The minimum energy pathways for the formation of the chelates are identified, showing the physical process through which cations can bind to one or two side chains of a glycolated polythiophene, with consequences for ion transport in bithiophene semiconductors.
Microstructured BN Composites with Internally Designed High Thermal Conductivity Paths for 3D Electronic Packaging
Authors: He Hongying , Peng Weixiang , Liu Junbo , Chan Xin Ying , Liu Shike , Lu Li , Le Ferrand Hortense 
Published: August 2022

AbstractMiniaturized and high‐power‐density 3D electronic devices pose new challenges on thermal management. Indeed, prompt heat dissipation in electrically insulating packaging is currently limited by the thermal conductivity achieved by thermal interface materials (TIMs) and by their capability to direct the heat toward heat sinks. Here, high thermal conductivity boron nitride (BN)‐based composites that are able to conduct heat intentionally toward specific areas by locally orienting magnetically functionalized BN microplatelets are created using magnetically assisted slip casting. The obtained thermal conductivity along the direction of alignment is unusually high, up to 12.1 W m−1 K−1, thanks to the high concentration of 62.6 vol% of BN in the composite, the low concentration in polymeric binder, and the high degree of alignment. The BN composites have a low density of 1.3 g cm−3, a high stiffness of 442.3 MPa, and are electrically insulating. Uniquely, the approach is demonstrated with proof‐of‐concept composites having locally graded orientations of BN microplatelets to direct the heat away from two vertically stacked heat sources. Rationally designing the microstructure of TIMs to direct heat strategically provides a promising solution for efficient thermal management in 3D integrated electronics.
Inkjet‐Printed Narrow‐Channel Mesoporous Oxide‐Based n‐Type TFTs and All‐Oxide CMOS Electronics
Authors: Devabharathi Nehru , Pradhan Jyoti Ranjan , Priyadarsini Sushree Sangita , Brezesinski Torsten , Dasgupta Subho 
Published: August 2022

AbstractOxide semiconductors are becoming the materials of choice for modern‐day display industries. The performance of solution‐processed oxide thin film transistors (TFTs) has also improved dramatically over the last few years. However, while oxygen deficient n‐type semiconductors can demonstrate excellent electronic transport, the performance of p‐type materials has remained unsatisfactory. Consequently, only the n‐type semiconductor‐based pseudo‐complementary metal oxide semiconductor (CMOS) technology has attracted tremendous interests recently; yet, the high power dissipation remains a problem. Here, this work demonstrates all‐oxide CMOS invertors with high‐performance narrow‐channel n‐type TFTs, which can compensate for the limited carrier mobility of the p‐type transistors. These n‐type TFTs are fabricated with polymer‐templated mesoporous In2O3 and with a device geometry that allows near‐vertical current transport, thereby rendering the TFT channel lengths to be equal to the semiconductor film thickness (≈50 nm). Unprecedented On‐current (1.02 mA µm−1) and transconductance (950 µS µm−1) are achieved. The CuO‐based p‐type TFTs also show a device mobility of no less than 0.5 cm2 V−1 s−1. The printed all‐oxide CMOS inverters are found to operate at very low supply voltages and demonstrate sharp transfer curves with maximum signal gain of 31 and low power dissipation of only 4 nW, at a supply voltage of 1 V.
Symmetric Thin Films Based on Silicon Materials for Angle‐Insensitive Full‐Color Structural Colors
Authors: Feng Kun , Li Qingyuan , Liu Jintong , Guan Peng , Yuan Jinliang , Cai Guangshi , Chen Nan , Bu Yikun 
Published: August 2022

AbstractHere, reflective full‐color structural colors with symmetrical thin film structures made from all silicon‐based materials are demonstrated. Considering practical application scenarios, the five‐layer reflection enhancement unit located in the core of the device is composed of amorphous silicon (a‐Si) and SiO2. Because of the large refractive index difference, the high reflection efficiency can be achieved, and the highest peak reflectivity of the sample can reach 89%. On both sides of the device, the same anti‐reflection (AR) unit composed of SiOx and SiO2 is deposited, which can significantly reduce the reflection of non‐target wavelength and enhance the color purity of the device. Meanwhile, the thin thickness of the absorbing materials provides the better angular insensitivity and the device shows a stable color appearance in the range of 0–60°. Based on the idea of symmetrical structure, a variety of angular insensitive structural colors can be realized. The scheme is simple in structure and material, which provides the feasibility for mass production. Particularly, the symmetry of the structure makes structural colors have unique advantages and the potential to be widely applied in the color paint fields of printing, decoration, and counterfeit detection.
Stable Flexible Transparent Electrodes for Localized Heating of Lab‐on‐a‐Chip Devices
Authors: Papanastasiou Dorina T. , Sekkat Abderrahime , Nguyen Viet Huong , Jiménez Carmen , Muñoz‐Rojas David , Bruckert Franz , Bellet Daniel 
Published: August 2022

AbstractIn situ biological observations require stable, accurate, and local temperature control of specimen. Several heating elements are coupled with microfluidic systems, but few of them are transparent to visible light and therefore compatible with microscopic observation. Traditional transparent electrodes, such as indium tin oxide, still suffer from high fabrication cost and brittleness, which is not fully compatible to emerging microfluidic devices. Here, a lightweight, low‐cost, flexible transparent heater based on percolating silver nanowire networks, protected with a transparent zinc oxide film, for the in situ monitoring of biological experiments is proposed. Using the fluorescence of dyes bound to double‐stranded DNA to monitor its temperature in situ, it is demonstrated that such nanocomposites allow rapid and reproducible heating under low applied voltage. Furthermore, selective heating is achieved in different zones of the same microchannel or for adjacent microchannels of the chip heating at different temperatures, with a single transparent heater and bias.
Advances in Emerging Photonic Memristive and Memristive‐Like Devices
Authors: Wang Wenxiao , Gao Song , Wang Yaqi , Li Yang , Yue Wenjing , Niu Hongsen , Yin Feifei , Guo Yunjian , Shen Guozhen 
Published: August 2022

AbstractPossessing the merits of high efficiency, low consumption, and versatility, emerging photonic memristive and memristive‐like devices exhibit an attractive future in constructing novel neuromorphic computing and miniaturized bionic electronic system. Recently, the potential of various emerging materials and structures for photonic memristive and memristive‐like devices has attracted tremendous research efforts, generating various novel theories, mechanisms, and applications. Limited by the ambiguity of the mechanism and the reliability of the material, the development and commercialization of such devices are still rare and in their infancy. Therefore, a detailed and systematic review of photonic memristive and memristive‐like devices is needed to further promote its development. In this review, the resistive switching mechanisms of photonic memristive and memristive‐like devices are first elaborated. Then, a systematic investigation of the active materials, which induce a pivotal influence in the overall performance of photonic memristive and memristive‐like devices, is highlighted and evaluated in various indicators. Finally, the recent advanced applications are summarized and discussed. In a word, it is believed that this review provides an extensive impact on many fields of photonic memristive and memristive‐like devices, and lay a foundation for academic research and commercial applications.
Positively Charged Pt‐Based Nanoreactor for Efficient and Stable Hydrogen Evolution
Authors: Feng Kun , Xu Jiabin , Chen Yufeng , Li Shuo , Kang Zhenhui , Zhong Jun 
Published: August 2022

AbstractPositively charged Pt can work as the active center for hydrogen evolution reaction (HER) but the corresponding design of state‐of‐the‐art electrocatalysts at high current densities has never been realized. Here the application of positively charged Pt in an effective Fe‐PtNiPO nanoreactor for highly efficient and stable HER is demonstrated. Synchrotron radiation X‐ray absorption spectroscopy confirms the formation of internal positively charged Pt and the in situ experiments reveal the quick charge transfer in the nanoreactor. Ni‐based materials around Pt are used to tune the electronic structure and promote the water dissociation to form locally enriched H+, while a porous Fe shell can both prevent the loss of active material and allow the efficient material transport. All the beneficial compositions work together to form an effective nanoreactor for HER. As a result, the Fe‐PtNiPO nanoreactor shows a low overpotential of 19 mV to achieve 10 mA cm−2 and exhibits a high mass activity of 10.93 A mgPt−1 (at 100 mV). Most importantly, it only needs an ultra‐low overpotential of 193 mV to achieve a high current density of 1000 mA cm−2 with an excellent stability over 300 h, which represents one of the best electrocatalysts for alkaline HER and might be used for large‐scale industrial application in the future.
Identification of serum microRNAs as potential diagnostic biomarkers for detecting precancerous lesions of gastric cancer
Authors: Otsu Hajime , Nambara Sho , Hu Qingjiang , Hisamatsu Yuichi , Toshima Takeo , Takeishi Kazuki , Yonemura Yusuke , Masuda Takaaki , Oki Eiji , Mimori Koshi 
Published: August 2022

AbstractAimGastric mucosal changes associated with chronic gastritis are known to be precancerous lesions of gastric cancer. We aimed to identify individuals with a high risk of gastric cancer by detection of microRNAs (miRNA) in the blood as biomarkers.MethodsOf 1206 individuals screened, 144 who were positive for Helicobacter pylori (H. pylori) by the serum antibody test and who underwent endoscopy were the subjects of this study. For the gross assessment of mucosal inflammation, we applied the Kimura–Takemoto classification, in which normal mucosa was defined as grade 0, and atrophy was categorized as grade 1 (C‐1 and C‐2), grade 2 (C‐3 and O‐1), and grade 3 (O‐2 and O‐3). Serum samples were divided into two phases and used for miRNA microarray profiling. We compared the expression of miRNAs in grade 3 mucosa and other grades. Expression in gastric cancer was confirmed with TCGA data.ResultsmiR‐196b‐3p was significantly upregulated, and miR‐92a‐2‐5p was downregulated (P < .05 and q < 0.2). TCGA data showed a high expression of miR‐196b‐3p in gastric cancer cases (P < .001). Comparing grade 3 and the others, the area under the receiver operating characteristic curve using the detected miRNAs was as high as about 0.7. Furthermore, the combination of miRNAs resulted in higher accuracy. In terms of the significance of the combinatory mRNAs, the combination of three miRNAs (miR‐196b‐3p, miR‐92a‐2‐5p, and miR‐6791‐3p) revealed high sensitivity and specificity, with the area under the curve exceeding 0.8.ConclusionThe identified combinatory miRNAs may represent promising biomarkers of precancerous lesions in gastric cancer.
Reductive Al−B σ‐Bond Formation in Alumaboranes: Facile Scission of Polar Multiple Bonds
Authors: Güven Zeynep , Denker Lars , Wullschläger Daniela , Pablo Martínez Juan , Trzaskowski Bartosz , Frank René 
Published: August 2022

AbstractWe present facile access to an alumaborane species with electron precise Al−B σ‐bond. The reductive rearrangement of 1‐(AlI2), 8‐(BMes2) naphthalene (Mes=2,4,6‐Me3C6H2) affords the alumaborane speciescyclo‐(1,8‐C10H6)‐[1‐Al(Mes)(OEt2)‐8‐B(Mes)] with a covalent Al−B σ‐bond. The Al−B σ‐bond performs the reductive scission of multiple bonds: S=C(NiPrCMe)2affords the naphthalene bridged motif B−S−Al(NHC), NHC=N‐heterocyclic carbene, while O=CPh2is deoxygenated to afford an B−O−Al bridged species with incorporation of the remaining ≡CPh2fragment into the naphthalene scaffold. The reaction with isonitrile Xyl‐N≡C (Xyl=2,6‐Me2C6H4) proceeds via a proposed (amino boryl) carbene species; which adds a second equivalent of isonitrile to ultimately form the Al−N−B bridged speciescyclo‐(1,8‐C10H6)‐[1‐Al(Mes)‐N(Xyl)‐8‐B{C(Mes)=C−N−Xyl}] with complete scission of the C≡N triple bond. The latter reaction is supported with isolated intermediates and by DFT calculations.
A new heterotrimetallic sandwich‐like CuII–LaIII–CuII (3d–4f–3d) cluster as a model anticancer drug in interaction with FS‐DNA and BSA and as a new artificial catalyst for catecholase activity
Authors: Keshavarzian Elahe , Asadi Zahra , Poupon Morgane , Dusek Michal , Rastegari Banafsheh 
Published: August 2022

A new heterotrimetallic sandwich‐like CuII–LaIII–CuII cluster, [(valpn)2Cu2La(NO3)2]NO3(H2O)1.8, (H2valpn = 1,3‐propanediylbis(2‐iminomethylene‐6‐methoxy‐phenol)), was synthesized by the reaction of [Cu(valpn)] with La (NO3)3.6H2O (1:1 M ratio) at room temperature. The resulted cluster was characterized by X‐ray diffraction, UV–Vis and IR spectroscopy, and elemental analysis (CHN). The crystal structure of the cluster revealed that La(III) ion was sandwiched between two [Cu(valpn)] moieties and located in the open compartments of two copper Schiff base complexes and being surrounded by 12 oxygen atoms. This cluster complex, as a model anticancer drug, was investigated in interaction with fish sperm deoxyribonucleic acid (FS‐DNA) using docking study and experimental methods such as fluorescence and UV–Vis spectroscopy, circular dichroism spectroscopy (CD), cyclic voltammetry (CV), viscosity measurements, and agarose gel electrophoresis. These investigations suggested intercalative interaction between the cluster complex and FS‐DNA. Plasma proteins are other targets for the anticancer drugs, so the cluster–bovine serum albumin (BSA) interaction was also investigated. For evaluating the binding, Stern–Volmer constants (KSV) and the number of binding sites (n) were calculated. It was proposed that the electrostatic interaction was the main force in the cluster–BSA binding. Cytotoxic activity was assayed by MTT assay toward LACaP, MCF‐7, and HeLa cancer cell lines. The IC50 values of the cluster for HeLa and LACaP cell lines were lower than for MCF‐7 cell lines. The docking studies were also performed for cluster–BSA and cluster–DNA interactions. The cluster was also investigated as an artificial enzyme in catechol oxidase activity, and kinetics of the oxidation of 3,5‐di‐tert‐butylcatechol catalyzed by the cluster was studied.
Enzyme activity inhibition properties of new cellulose nanocrystals from Citrus medica L. pericarp: A perspective of cholesterol lowering
Authors: Kalhori Fateme , Yazdyani Helya , Khademorezaeian Fatemeh , Hamzkanloo Negar , Mokaberi Parisa , Hosseini Sare , Chamani Jamshidkhan 
Published: August 2022

AbstractAs a waste material, the amazing potential of cellulose nanocrystals (CNCs) isolated from Citrus medica L. pericarp in being a natural resource of lingo‐cellulosic products has never been investigated before. In the present study, an alkaline pretreatment and a two‐step bleaching procedure were applied to conduct the desired acid hydrolysis by the usage of 64% sulfuric acid at 50°C for 105 min. The extracted CNCs were distinguished through the means of transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), X‐ray diffraction (XRD), atomic force microscopy (AFM), Fourier‐transform infrared (FTIR) spectroscopy, dynamic light scattering (DLS), zeta potential, and energy‐dispersive X‐ray spectroscopy (EDX). The elimination of peaks, which were accountable for the inducement of hemicelluloses and lignin, was confirmed by the FTIR results and were also validated by the outcomes of XRD that proved the gentle removal of non‐cellulosic components. The morphology and size of CNCs were indicated through the FESEM and TEM results. In addition, the spherical forms of synthesized CNCs were observed with a diameter of 46 nm throughout the FESEM images, while displaying a value of 42.54 nm as well due to TEM micrographs. The obtained zeta potential displayed a reasonable negative surface charge for CNCs. Furthermore, the cytotoxicity assessment of this product on fibroblast cells was performed to study their susceptibility for bio‐medical and cosmetic industrial applications, which resulted in the lack of exhibiting any cytotoxic effects. In conformity to the outcomes of TEM and FESEM, the results of AFM revealed a fine dispersion and spherical form of cellulose nanoparticles. The interaction between HMG‐CoA reductase and CNC was studied by the usage of multi‐spectroscopic methods and enzyme kinetics to explore the binding mechanism of HMG‐CoA reductase–CNC system. Reduced catalytic activity of the occurrence of changes in the secondary structure of HMG‐CoA reductase was as a result of interacting with CNC causing a reduction in its catalytic activity.
“Guide” of muscone modification enhanced brain‐targeting efficacy and anti‐glioma effect of lactoferrin modified DTX liposomes
Authors: Qi Na , Duan Wenjuan , Gao Duan , Ma Ningzhu , Zhang Jianguo , Feng Jianfang , Li Aimin 
Published: August 2022

AbstractGlioma is one of the most aggressive malignant diseases for human health. It is difficult to resect completely due to their invasiveness. The targeted delivery, as a noninvasive approach, is a major strategy for the development of treatments for brain tumors. Lactoferrin (Lf) receptors are over‐expressed in both brain endothelial cells and glioma cells. Macromolecular Lf modified nanoparticles have been shown to enhance the brain targeting. Muscone is a “guide” drug that have been demonstrated to promote liposomes into the brain by modification. To further enhance the brain‐targeting efficacy of Lf modified carriers, we designed that Lf and muscone dual‐modified liposomes cross blood–brain barrier (BBB) and target to brain for enhanced docetaxel (DTX) brain delivery. The results showed that we successfully prepared Lf and muscone dual‐modified liposomes (Lf‐LP‐Mu‐DTX), the number of Lf molecules connected to the surface of per liposome was 28. Lf‐LP‐Mu‐DTX increased uptake in both U87‐MG cells and hCMEC/D3 cells, enhanced penetration of U87‐MG tumor spheroid and in vitro BBB model, had better in vitro and in vivo anti‐tumor effects. In conclusion, “guide” of muscone modification enhanced brain‐targeting efficacy of Lf modified liposomes, Lf and muscone dual‐modified docetaxel loaded liposomes present a potential brain‐targeting drug delivery system for use in the future treatment of gliomas.
Cationic Gold(II) Complexes: Experimental and Theoretical Study**
Authors: Mehara Jaya , Koovakattil Surendran Adarsh , van Wieringen Teun , Setia Deeksha , Foroutan‐Nejad Cina , Straka Michal , Rulíšek Lubomír , Roithová Jana 
Published: August 2022

AbstractGold(II) complexes are rare, and their application to the catalysis of chemical transformations is underexplored. The reason is their easy oxidation or reduction to more stable gold(III) or gold(I) complexes, respectively. We explored the thermodynamics of the formation of [AuII(L)(X)]+complexes (L=ligand, X=halogen) from the corresponding gold(III) precursors and investigated their stability and spectral properties in the IR and visible range in the gas phase. The results show that the best ancillary ligands L for stabilizing gaseous [AuII(L)(X)]+complexes are bidentate and tridentate ligands with nitrogen donor atoms. The electronic structure and spectral properties of the investigated gold(II) complexes were correlated with quantum chemical calculations. The results show that the molecular and electronic structure of the gold(II) complexes as well as their spectroscopic properties are very similar to those of analogous stable copper(II) complexes.
Vibrational Circular Dichroism Unravels Supramolecular Chirality and Hydration Polymorphism of Nucleoside Crystals
Authors: Krupová Monika , Leszczenko Patrycja , Sierka Ewa , Emma Hamplová Sára , Pelc Radek , Andrushchenko Valery 
Published: August 2022

AbstractVibrational circular dichroism (VCD) spectroscopy has been widely used to study (bio)molecules in solution. However, its solid‐state applications have been restricted due to experimental limitations and artifacts. Having overcome some of them, the first VCD study of nucleoside crystals is now presented. A two‐orders‐of‐magnitude enhancement of VCD signal was observed due to high molecular order in the crystals and resulting supramolecular chirality. This allowed to obtain high‐quality VCD spectra within minutes using minute amounts of samples. The VCD technique is extremely sensitive in detecting changes in a crystal order and is able to distinguish different hydration states of crystals. This elevates it to a new level, as a fast and efficient tool to study chiral crystalline samples. This study demonstrates that VCD is capable of near‐instantaneous detection of hydration polymorphs and crystal degradation, which is of substantial interest in pharmaceutical industry (quality and stability control).
Dioxygen Activation by Redox‐Active Bis(aldimine) Ligand Bridged Diruthenium Complex Possessing Singlet Ground State
Authors: Biswas Mitrali , Dey Sanchaita , Das Abhishek , Kanti Paine Tapan , Panda Sanjib , Kumar Lahiri Goutam 
Published: August 2022

AbstractThe unexplored ‘actor’ behavior of redox‐active bis(aldimine) congener, p‐phenylene‐bis(picoline)aldimine (L1), towards dioxygen activation and subsequent functionalization of its backbone was demonstrated on coordination with {Ru(acac)2} (acac= acetylacetonate). Reaction under aerobic condition led to the one‐pot generation of dinuclear complexes with unperturbed L1, imino‐carboxamido (L2−), and bis(carboxamido) (L32−)‐bridged isovalent {RuII(μ‐L1)RuII}, 1/ {RuIII(μ‐L32−)RuIII}, 3 and mixed‐valent {RuII(μ‐L2−)RuIII}, 2. Authentication of the complexes along with the redox non‐innocence behavior of their bridge have been validated through structure, spectroelectrochemistry and DFT calculations. Kinetic and isotope labelling experiments together with DFT analyzed transition states justified the consideration of redox shuttling at metal/L1 interface for 3O2 activation despite of the closed shell configuration of 1 (S=0) to give carboxamido derived 2/3.