bluuebunny/crossref_metadata_2025 huggingface dataset:
Induced Birefringence in 3D Printing: Concealing Information Optically within Printed Objects
Authors: Roper David M. , Kwon Kyung‐Ah , Malone Luke P. , Best Serena M. , Cameron Ruth E.
Published: May 2022

This paper presents a novel method to spatially vary the intra‐layer birefringence of Fused Filament Fabricated (FFF) parts by controlling chain alignment during extrusion along individual rasters. The role of print speed, extrusion factor and layer separation on the birefringence of single PLLA layers is explored, at thicknesses ranging from 50–125 µm and print speeds 1000–6000 mm min−1. The cumulative and subtractive effect of multiple PLLA layers are explored to elicit colours corresponding to a range of retardations, achieve complete extinction, and printing a physical Michel‐Levy chart. By increasing print speed and reducing layer separation and extrusion factor, a birefringence up to Δn = 9 × 10−4 could be achieved in single layers. In multi‐layer structures, retardations of 0–800 nm are demonstrated. These results suggest that spatially varied birefringence can be used to store data, text or images, which can be resolved when parts are illuminated between polarizers. This effect is utilized to present a steganographic technique embedding information within bulk printed parts. These techniques might find application in a range of printed optics and devices, where spatial control over molecular alignment and associated influence on the propagation of light is desirable, including the ability to encode information within a print.
Improved Efficiency of Light‐Emitting Diodes by Plasmonic Nanopatterning of the Charge‐Transfer Layer
Authors: Lin Lyuye , Krahne Roman , Proietti Zaccaria Remo
Published: May 2022

Light‐emitting diodes (LEDs) are presently not exploited at their full potential due to a multiple range of detrimental effects, such as generation of local modes, either surface plasmon‐like or optical modes, ohmic losses, or total internal reflection caused by refractive index mismatch. Herein, the authors focus on LEDs with layered architectures by investigating the effects of interface nanopatterning occurring in the electron‐transport layer on their overall performance. In particular, the integration of photonic nanostructures is investigated, while leaving the optical properties of the emitting material unchanged. The numerical results show that specifically designed nanopatterning can strongly contribute to the enhancement of the Purcell factor, outcoupling efficiency and thereby increase the external quantum efficiency by a factor of 2 with respect to the unpatterned structures. This demonstrates that, as in other light‐emission technologies, morphological patterning is a valid strategy to improve the performance of LEDs.
Formation of N−P(O)−S Bonds from White Phosphorus via a Four‐Component Reaction
Authors: Zhang Yue , Cao Yinwei , Chi Yangyang , Chen Shuanghui , Zeng Xiangzhe , Liu Yan , Tang Guo , Zhao Yufen
Published: May 2022

Functionalization of white phosphorus with disulfides, amines and KOH to phosphoramidodithioates containing both P−N, P−S and P=O bonds via a four‐component reaction is presented. It proceeds with high yields and provides an attractive approach for the construction of valuable N−P(O)−S motif using a one‐step strategy. The advantages of this newly developed process include a clean reaction profile, complete conversion of white phosphorus, transition metal‐free and halogen‐free environmentally benign system, and large‐scale synthetic application. Besides, phosphoramidodithioates can also be utilized to construct P−C, P−O and P=S bonds with the appropriate reagents.

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Ultrasensitive Molecular Detection at Subpicomolar Concentrations by the Diffraction Pattern Imaging with Plasmonic Metasurfaces and Convex Holographic Gratings
Authors: Wu Mingxi , Li Guohua , Ye Xiangyi , Zhou Bin , Zhou Jianhua , Cai Jingxuan
Published: May 2022

Compact and cost‐effective optical devices for highly sensitive detection of trace molecules are significant in many applications, including healthcare, pollutant monitoring and explosive detection. Nanophotonic metasurface‐based sensors have been intensively attracting attentions for molecular detection. However, conventional methods often involve spectroscopic characterizations that require bulky, expensive and sophisticated spectrometers. Here, a novel ultrasensitive sensor of plasmonic metasurfaces is designed and fabricated for the detection of trace molecules. The sensor features a convex holographic grating, of which the first‐order diffraction pattern of a disposable metasurface is recorded by a monochrome camera.The diffraction pattern changes with the molecules attached to the metasurface, realizing label‐free and spectrometer‐free molecular detection by imaging and analyzing of the diffraction pattern. By integrating the sensor with a microfluidic setup, the quantitative characterization of rabbit anti‐human Immunoglobulin G (IgG) and human IgG biomolecular interactions is demonstrated with an excellent limit of detection (LOD) of 0.6 pm. Moreover, both the metasurface and holographic grating are obtained through vacuum‐free solution‐processed fabrications, minimizing the manufacturing cost of the sensor. A prototype of the imaging‐based sensor, consisting of a white light‐emitting diode (LED) and a consumer‐level imaging sensor is achieved to demonstrate the potential for on‐site detection.
Bioresorbable Nanostructured Chemical Sensor for Monitoring of pH Level In Vivo
Authors: Corsi Martina , Paghi Alessandro , Mariani Stefano , Golinelli Giulia , Debrassi Aline , Egri Gabriella , Leo Giuseppina , Vandini Eleonora , Vilella Antonietta , Dähne Lars , Giuliani Daniela , Barillaro Giuseppe
Published: May 2022

Here, the authors report on the manufacturing and in vivo assessment of a bioresorbable nanostructured pH sensor. The sensor consists of a micrometer‐thick porous silica membrane conformably coated layer‐by‐layer with a nanometer‐thick multilayer stack of two polyelectrolytes labeled with a pH‐insensitive fluorophore. The sensor fluorescence changes linearly with the pH value in the range 4 to 7.5 upon swelling/shrinking of the polymer multilayer and enables performing real‐time measurements of the pH level with high stability, reproducibility, and accuracy, over 100 h of continuous operation. In vivo studies carried out implanting the sensor in the subcutis on the back of mice confirm real‐time monitoring of the local pH level through skin. Full degradation of the pH sensor occurs in one week from implant in the animal model, and its biocompatibility after 2 months is confirmed by histological and fluorescence analyses. The proposed approach can be extended to the detection of other (bio)markers in vivo by engineering the functionality of one (at least) of the polyelectrolytes with suitable receptors, thus paving the way to implantable bioresorbable chemical sensors.
Salt‐Inducible Kinase 2‐Triggered Release of Its Inhibitor from Hydrogel to Suppress Ovarian Cancer Metastasis
Authors: Hua Yue , Yin Han , Liu Xiaoyang , Xie Jinbing , Zhan Wenjun , Liang Gaolin , Shen Yang
Published: May 2022

Salt‐inducible kinase 2 (SIK2) is a promising target for ovarian cancer therapy due to its critical role in tumorigenesis and progression. Currently available SIK2 inhibitors have shown remarkable therapeutic effects on ovarian cancers in preclinical studies. However, direct administration of the SIK2 inhibitors may bring significant off‐target effect, limiting their clinical applications. In this work, by rational design of a hydrogelator Nap‐Phe‐Phe‐Glu‐Glu‐Leu‐Tyr‐Arg‐Thr‐Gln‐Ser‐Ser‐Ser‐Asn‐Leu‐OH (Nap‐S) to coassemble a SIK2 inhibitor HG‐9‐91‐01 (HG), a SIK2‐responsive supramolecular hydrogel (Gel Nap‐S+HG) for local administration and SIK2‐responsive release of HG is reported to efficiently suppress ovarian cancer metastasis. Under the activation of SIK2 overexpressed in ovarian cancers, Nap‐S in the hydrogel is phosphorylated to yield hydrophilic Nap‐Phe‐Phe‐Glu‐Glu‐Leu‐Tyr‐Arg‐Thr‐Gln‐Ser(H2PO3)‐Ser‐Ser‐Asn‐Leu (Nap‐Sp), triggering the disassembly of the hydrogel and a responsive release of the inhibitor. Cell experiments indicate that sustained release of HG from Gel Nap‐S+HG induce a prominent therapeutic effect on cancer cells by inhibiting SIK2 and phosphorylation of their downstream signaling molecules. Animal experiments demonstrate that, compared with those tumor model mice treated with free HG, Gel Nap‐S+HG‐treatment mice show an enhanced inhibition on ovarian tumor growth and metastasis. It is anticipated that the Gel Nap‐S+HG can be applied for ovarian cancer therapy in clinic in the near future.
Food retail profits, competition, and the Great Recession
Authors: Cleary Rebecca , Chenarides Lauren
Published: May 2022

We investigate the competitive effects of entry in the food retail sector in nonmetropolitan counties in the United States from 1998 to 2014. We pay particular attention to the period that covers the Great Recession, which disrupted market structure across a number of industries. Using a county‐level panel dataset, we use a seminal entry model to infer the local competitive effects of entry in the food retail sector. We estimate entry thresholds over time, which we then use to describe the rate of decline in profit margins following subsequent entry via entry threshold ratios. We find that food retail firms required a smaller market size to break even during the Great Recession, perhaps pointing to higher profits, as consumers shifted purchases to food‐at‐home. This effect is short‐lived for all but a single firm. The market threshold required to support a single food retail firm remains low throughout the post‐recession recovery period. We also find that the second firm may not decrease profit margins, but that competition increases meaningfully with the third and fourth entrants. The increased competition during the Great Recession also appears to have persisted into the recovery period. [EconLit Citations: L18; Q18].
Micrometastasis in lymph nodes of colorectal cancer
Authors: Yamamoto Hirofumi
Published: May 2022

Colorectal cancer (CRC) is one of the most common cancers worldwide. Postoperative adjuvant chemotherapy is recommended for node‐positive stage III patients. A systematic meta‐analysis reported that the presence of micrometastases in regional lymph nodes (LNs) was associated with poor survival in patients with node‐negative CRC. Because most data employed in the meta‐analysis were based on retrospective studies, we conducted a prospective clinical trial and concluded that stage II is a transitional zone between stage I and stage III, where CRC tumors continuously increase the micrometastasis volume in LNs and proportionally raise the risk for tumor recurrence. The one‐step nucleic acid amplification (OSNA) assay is a simple and rapid technique to detect CK19 mRNA using the reverse‐transcription loop‐mediated isothermal amplification (RT‐LAMP) method. Using the OSNA assay, we and colleagues reported that the upstaging rates of pStages I, IIA, IIB, and IIC were 2.0%, 17.7%, 12.5%, and 25%, respectively, in 124 node‐negative patients. Survival analysis indicated that OSNA positive stage II CRC patients had a shorter 3‐y disease‐free survival rate than OSNA negative stage II CRC patients. In 2017, AJCC TNM staging (the 8th version) revised the definition of LN metastasis in colon cancer and it is stated that micrometastasis should be considered as a standard LN metastasis. To our surprise, this revision was based on a meta‐analysis to which our previous study on micrometastasis largely contributed. The remaining questions to be addressed are how to find micrometastases efficiently and whether postadjuvant chemotherapy is effective to prevent disease recurrence and to contribute to longer survival.
Knitting Shape‐Memory Alloy Wires for Riding a Robot: Constraint Matters for the Curvilinear Actuation
Authors: Wu Tian-Yue , Fang Qian-Yi , Xu Zhu-Long , Li Xin-Jin , Ma Wen-Xuan , Chu Ming-Shuai , Lim Jae Hyuk , Chuang Kuo-Chih
Published: May 2022

To allow a linear one‐way shape‐memory alloy (SMA) wire to have a deterministic curvilinear two‐way actuation, the SMA wire can be bonded on a curved substrate or prestrained soft materials to create mismatched SMA‐wire composites. These composites have recently been applied to soft robots to achieve rapid periodic untethered locomotion. Herein, by knitting bare SMA wires on scattered holes, it is shown that the substrate‐free knitted SMA wires can periodically ride robots forward, where a deterministic spatial curvilinear actuation can be achieved in which its in‐between heated configuration and the final stable pattern is sensitive to the prescribed hole constraints. By arranging “knitting‐constraints,” the 3D‐printed and origami robots with a pair of SMA wires, respectively, are ridden. The SMA wires have an angle parameter with a variation range of 30° for the 3D‐printed robot and that of 8° for the origami robot, where the angle parameter is defined to indicate the performance of the knitted SMAs. Both the robots can displace up to 5 mm in one motion cycle with an average speed of 20 and 15 mm min−1, respectively. The motion efficiencies of the two robots are close to 1 when taking the possible backward movement in one forward‐moving cycle into consideration.
Novel phosphopantothenoylcysteine synthetase (PPCS) mutations with prominent neuromuscular features: Expanding the phenotypical spectrum of PPCS‐related disorders
Authors: Lok Aishin , Fernandez‐Garcia Miguel A. , Taylor Robert W. , French Courtney , MacFarland Robert , Bodi Istvan , Champion Michael , Josifova Dragana , Raymond Frances Lucy , Iuso Arcangela , Jungbluth Heinz , Milan Anna , Singh Rahul R.
Published: May 2022

Biallelic pathogenic variants in phosphopantothenoylcysteine synthetase, PPCS, are a rare cause of a severe early‐onset dilated cardiomyopathy with high morbidity and mortality. To date, only five individuals with PPCS‐mutations have been reported. Here, we report a female infant who presented in the neonatal period with hypotonia, a necrotizing myopathy with intermittent rhabdomyolysis and other extracardiac manifestations before developing a progressive and ultimately fatal dilated cardiomyopathy. Gene agnostic trio genome sequencing revealed two rare variants in the PPCS [MIM: 609853] in trans, a previously reported pathogenic c.320_334del p. (Pro107_Ala111del) variant, and a c.613‐3C>G intronic variant of uncertain significance. Functional studies confirmed the likely pathogenicity of this variant. Our case provides clinical and histopathological evidence for an associated neuromuscular phenotype not previously recognized and expands the evolving phenotypic spectrum of PPCS‐related disorders. We also performed a literature search of all previously published cases and summarize the common features.
Mono‐N‐Alkylation of Sulfonamides with Alcohols Catalyzed by Iridium N‐Heterocyclic Carbene‐Phosphine Complexes
Authors: Li Xingzhen , Peters Bram B. C. , Tan Min , He Lei , Yang Jianping , Andersson Pher G. , Zhou Taigang
Published: May 2022

A N‐heterocyclic carbene‐phosphine iridium complex is presented for the efficient and selective mono‐N‐alkylation of sulfonamides with alcohols based on a borrowing hydrogenation strategy. Herein, water is the only by‐product and this methodology thus offers a more environmentally benign and interesting alternative to the use of traditional alkylating reagents. This facile protocol tolerates a large number of (hetero) aromatic and aliphatic sulfonamides as well as (hetero) aromatic and aliphatic alcohols to obtain the desired product is high isolated yield (up to 98%). The alkylation completely retards after the formation of the secondary sulfonamide and no over‐alkylation was observed in all cases. The option to run the reaction under solvent‐free conditions as well as the scalability of this borrowing hydrogenation are key features of this protocol.
Henry Cavendish on Gravitational Deflection of Light
Authors: Lotze Karl‐Heinz , Simionato Silvia
Published: May 2022

A recent analysis of two handwritten sheets of paper by Henry Cavendish (1731–1810) reveals the details of his calculation of the deflection of light induced by the gravitational field of isolated celestial bodies. Except for a few lines from one of these pages, where Cavendish communicated the result, the two documents have never been published. This gave rise to speculations about how, if at all, Cavendish derived his formula for the deflection angle by his own calculations. Such doubts are dispelled and it is demonstrated how Cavendish, in these documents, applied Newtonian mechanics to the corpuscles of light.
Alternating Terpolymers through Cyclopolymerization and Subsequent Orthogonal Functionalization
Authors: Gerdt Philipp , Studer Armido
Published: May 2022

A method for the synthesis of functionalized alternating copolymers by reversible deactivation radical polymerization was developed. Copolymerization by reversible addition–fragmentation chain transfer of hexenyl vinyl ether with a novel fluorinated divinyl monomer yields alternating cyclopolymers that can be chemoselectively modified by three distinct orthogonal functionalization reactions. Along the thiol‐ene click reaction and amidation, a third functionalization was achieved via NHC‐catalyzed transesterification or acylation resulting in a small library of ABC‐type alternating terpolymers.
Optimization of highly dispersible silica/carbon black hybrid filler ratio for tire tread based on solution‐ andemulsion‐styrenebutadiene rubber
Authors: Thaptong Puchong , Sae‐Oui Pongdhorn , Jittham Pairote , Sirisinha Chakrit
Published: May 2022

In this study, the effects of hybrid filler ratio and styrene‐butadiene rubber (SBR) type on tire tread performance that is, wet grip (WG), fuel‐saving efficiency (FSE), and abrasion resistance, were focused. Two types of SBR that is solution‐SBR (S‐SBR) and emulsion‐SBR (E‐SBR) were selected and reinforced by various ratios of highly dispersible silica (HDSi) to carbon black (CB). Although increasing the CB ratio had negative effects on WG, FSE, heat build‐up, and dynamic set, it improved abrasion resistance. Results revealed a good balance of tire performance at a CB ratio of 40 wt%. Clearly, S‐SBR provided better overall tire performance than E‐SBR, particularly in the silica‐filled system. This is possibly due to the higher glass transition temperature (Tg) and the greater magnitudes of rubber‐filler interaction and crosslink density of S‐SBR. Surprisingly, the HDSi/CB hybrid ratio and the SBR type had little influence on the degree of filler dispersion, probably because of the sufficiently long mixing time employed in this experiment.
Effects of ammonium persulfate on coconut wood (Cocos nucifera L.) cellulose, hemicellulose, and lignin polymers: Improved sound absorption capacity
Authors: Kolya Haradhan , Jang Eun‐Suk , Hashitsume Kazuharu , Kang Chun‐Won
Published: May 2022

The rational design of sound absorption boards made of wood materials is an attractive field of research. This article describes a simple and low‐cost ammonium persulfate treatment on coconut wood cell walls (Cocos nucifera L.). Reaction parameters such as concentration of reactant and reaction time were optimized. The results of different instrumental characterization such as X‐ray photoelectron spectroscopy, X‐ray diffraction, attenuated total reflectance–Fourier transforms infrared spectroscopy, and scanning electron microscope supports the chemical alterations of the wood cell wall. The quantitative analysis of hemicellulose, cellulose, and lignin was performed. The significant changes in cell‐walls enhanced average sound absorption coefficient at each frequency range: 60.4% at 500–1000 Hz (t = −10.593 and p < 0.001), 80.8% at 1000–2000 Hz (t = −4.798 and p < 0.001), 96.2% at 2000–4000 Hz (t = −58.527 and p < 0.001) and 83.0% at 500–64000 Hz (t = −51.261 and p < 0.001). It is due to the increment of gas permeability (288.3%, p = <0.001). These results could be beneficial for new research on wood‐based sound absorption materials to regulate the acoustic environment in houses.
3D‐QSAR and scaffold hopping based designing of benzo[d]ox‐azol‐2(3H)‐one and 2‐oxazolo[4,5‐b]pyridin‐2(3H)‐one derivatives as selective aldehyde dehydrogenase 1A1 inhibitors: Synthesis and biological evaluation
Authors: Verma Himanshu , Narendra Gera , Raju Baddipadige , Kumar Manoj , Jain Subheet K. , Tung Gurleen K. , Singh Pankaj K. , Silakari Om
Published: May 2022

Aldehyde dehydrogenase 1 (ALDH1A1), an oxidoreductase class of enzymes, is overexpressed in various types of cancer cell lines and is the major cause of resistance to the Food and Drug Administration (FDA)‐approved drug, cyclophosphamide (CP). In cancer conditions, CP undergoes a sequence of biotransformations to form an active metabolite, aldophosphamide, which further biotransforms to its putative cytotoxic metabolite, phosphoramide mustard. However, in resistant cancer conditions, aldophosphamide is converted into its inactive metabolite, carboxyphosphamide, via oxidation with ALDH1A1. Herein, to address the issue of ALDH1A1 mediated CP resistance, we report a series of benzo[d]oxazol‐2(3H)‐one and 2‐oxazolo[4,5‐b]pyridin‐2(3H)‐one derivatives as selective ALDH1A1 inhibitors. These inhibitors were designed using a validated 3D‐quantitative structure activity relationship (3D‐QSAR) model coupled with scaffold hopping. The 3D‐QSAR model was developed using reported indole‐2,3‐diones based ALDH1A1 inhibitors, which provided field points in terms of electrostatic, van der Waals and hydrophobic potentials required for selectively inhibiting ALDH1A1. The most selective indole‐2,3‐diones‐based compound, that is, cmp 3, was further considered for scaffold hopping. Two top‐ranked bioisosteres, that is, benzo[d]oxazol‐2(3H)‐one and 2‐oxazolo[4,5‐b]pyridin‐2(3H)‐one, were selected for designing new inhibitors by considering the field pattern of 3D‐QSAR. All designed molecules were mapped perfectly on the 3D‐QSAR model and found to be predictive with good inhibitory potency (pIC50 range: 7.5–6.8). Molecular docking was carried out for each designed molecule to identify key interactions that are required for ALDH1A1 inhibition and to authenticate the 3D‐QSAR result. The top five inhibitor‐ALDH1A1 complexes were also submitted for molecular dynamics simulations to access their stability. In vitro enzyme assays of 21 compounds suggested that these compounds are selective toward ALDH1A1 over the other two isoforms, that is, ALDH2 and ALDH3A1. All the compounds were found to be at least three and two times more selective toward ALDH1A1 over ALDH2 and ALDH3A1, respectively. All the compounds showed an IC50 value in the range of 0.02–0.80 μM, which indicates the potential for these to be developed as adjuvant therapy for CP resistance.
Effect of Ligand Chain Length for Tuning of Molecular Dimensionality and Magnetic Relaxation in Redox Active Cobalt(II) EDOT Complexes (EDOT=3,4‐Ethylenedioxythiophene)
Authors: Ghosh Subrata , Kamilya Sujit , Mehta Sakshi , Herchel Radovan , Kiskin Mikhail , Veber Sergey , Fedin Matvey , Mondal Abhishake
Published: May 2022

Four cobalt(II) complexes, [Co(L1)2(NCX)2(MeOH)2] (X=S (1), Se (2)) and {[Co(L2)2(NCX)2]}n (X=S (3), Se (4)) (L1=2,5‐dipyridyl‐3,4,–ethylenedioxylthiophene and L2=2,5‐diethynylpyridinyl‐3,4‐ethylenedioxythiophene), were synthesized by incorporating ethylenedioxythiophene based redox‐active luminescence ligands. All these complexes have been well characterized using single‐crystal X‐ray diffraction analyses, spectroscopic and magnetic investigations. Magneto‐structural studies showed that 1 and 2 adopt a mononuclear structure with CoN4O2 octahedral coordination geometry while 3 and 4 have a 2D [4×4] rhombic grid coordination networks (CNs) where each cobalt(II) center is in a CoN6 octahedral coordination environment. Static magnetic measurements reveal that all four complexes displayed a high spin (HS) (S=3/2) state between 2 and 280 K which was further confirmed by X‐band and Q‐band EPR studies. Remarkably, along with the molecular dimensionality (0D and 2D) the modification in the axial coligands lead to a significant difference in the dynamic magnetic properties of the monomers and CNs at low temperatures. All complexes display slow magnetic relaxation behavior under an external dc magnetic field. For the complexes with NCS− as coligand observed higher energy barrier for spin reversal in comparison to the complexes with NCSe− as coligand, while mononuclear complex 1 exhibited a higher energy barrier than that of CN 3. Theoretical calculations at the DFT and CASSCF level of theory have been performed to get more insight into the electronic structure and magnetic properties of all four complexes.
Exploring the intercalation binding of tiamulin with DNA using multispectroscopy and a molecular modelling approach
Authors: Bi Shuyun , Li Xu , Ren Zhixin , Yang Bin , Wang Yuting , Zhang Fengming , Yuan Yue , Shao Di , Zhao Rui
Published: May 2022

The binding of tiamulin with calf thymus DNA was systematically investigated using multispectroscopy and molecular modelling techniques. For DNA, once tiamulin was added, viscosity (η) and melting temperature (Tm) both exhibited an uptrend. The fluorescence performance of the tiamulin–DNA complex did not change with the ionic strength changes. The binding constant (Ka) of tiamulin for single‐stranded DNA (ssDNA, 1.48 × 104 M−1) was obviously higher than that for double‐stranded DNA (dsDNA, 9.51 × 103 M−1) at 291 K. The helix structure became looser and the base stack force became stronger for DNA due to the presence of tiamulin as seen from circular dichroic (CD) spectra. The intercalation binding mode of tiamulin with DNA was disclosed. Molecular modelling also revealed tiamulin inserting into the base pairs with the lowest binding free energy of −18.73 kJ mol−1 using van der Waals forces as well as hydrogen bonds.
Understanding the role of non‐Watson‐Crick base pairs in DNA–protein recognition: Structural and energetic aspects using crystallographic database analysis and quantum chemical calculation
Authors: Das Soumi , Roy Siddhartha , Bhattacharyya Dhananjay
Published: May 2022

Specific recognition of DNA base sequences by proteins is vital for life‐cycles of all organisms. In a large number of crystal structures of protein–DNA complexes, DNA conformation significantly deviates from the canonical B‐DNA structure. A key question is whether such alternate conformations exist prior to protein binding and one is selected for complexation or the structure observed is induced by protein binding. Non‐canonical base pairs, such as Hoogsteen base pairs, are often observed in crystal structures of protein–DNA complexes. We decided to explore whether the occurrence of such non‐canonical base pairs in protein–DNA complexes is induced by the protein or is selected from pre‐existing conformations. Detailed quantum chemical calculations with dispersion‐corrected density functional theory (DFT‐D) indicated that most of the non‐canonical base pairs with DNA bases are stable even in the absence of the interacting amino acids. However, the G:G Hoogsteen base pair, which also appears in the telomere structure, appears to be unstable in the absence of other stabilizing agents, such as positively charged amino acids. Thus, the stability of many of the non‐canonical base pair containing duplexes may be close to the canonical B‐DNA structure and hence energetically accessible in the ground state; suggesting that the selection from pre‐existing conformations may be an important mechanism for observed non‐canonical base pairs in protein–DNA complexes.
The ‘need for speed’: Towards circular disruption—What it is, how to make it happen and how to know it's happening
Authors: Blomsma Fenna , Bauwens Thomas , Weissbrod Ilka , Kirchherr Julian
Published: May 2022

The environmental, social and economic limits and shortcomings of the current linear model of production and consumption highlight the necessity of a rapid transition towards a sustainable paradigm. The concept of a circular economy has recently gained traction among scholars, policy‐makers and businesses as a promising alternative. Yet our understanding of how to speed up the systemic transition from a linear economy paradigm towards a circular economy paradigm is lacking. In this paper, we address this research gap by introducing the concept of ‘circular disruption’ and by describing how such a disruption may unfold. To do so, we build on S‐curve thinking and the concept of panarchy. Based on the resulting synthesis, we propose three phases that constitute the core of the disruption process: (1) the release phase, (2) the reorganisation phase and (3) the eruption phase. We then operationalise these three phases for different enabling innovation system functions and illustrate our observations with examples for the textile and fashion sector. We discuss how each of the three disruption phases can be accelerated to quickly create an opening for the new circular paradigm. The proposed circular disruption framework offers novel insights on socio‐technical transitions and changes and contributes to strengthening a systemic and theoretically grounded approach to circular economy research. Scholars and practitioners alike may take advantage of this work to focus circular economy efforts on speed and scale—an urgently needed focus to start tackling the sustainability challenges humankind is currently facing.
Structural Diversity of Complex Phloroglucinol Derivatives from Eucalyptus Species
Authors: Faezeh Taghizadeh Seyedeh , Panahi Ali , Esmaeilzadeh Kashi Marziyeh , Kretschmer Nadine , Asili Javad , Ahmad Emami Seyed , Azizi Majid , Shakeri Abolfazl
Published: May 2022

Several species of the genus Eucalyptus are used in many traditional medicine systems for the treatment of respiratory tract infections, colds, flu, sore throats, and bronchitis. The genus Eucalyptus (Myrtaceae) is a well‐known natural source of bioactive phloroglucinols. These polyphenolic compounds bear an aromatic phenyl ring with three hydroxy groups (1,3,5‐trihydroxybenzene) which have been exhibiting a variety of biological activities such as antimicrobial, anticancer, anti‐allergic, anti‐inflammatory, and antioxidant activities. This review summarizes the literature published from 1997 until the end of 2021 and addresses the structure diversity of phloroglucinols isolated from Eucalyptus species and their biological activities. Phloroglucinol‐terpene adducts are the main class of compounds that have been reported in this genus.
Robotically performed diagnostic coronary angiography
Authors: Joseph Timothy , VanOosterhout Stacie , Negash Araya , VanLoo Lisa , Redmond Meaghan , Parker Jessica L. , McNamara David A. , Madder Ryan D.
Published: May 2022

Objective

This study was performed to investigate the efficacy and safety of robotic diagnostic coronary angiography.

Background

Robotic percutaneous coronary intervention is associated with marked reductions in physician radiation exposure. Development of robotic diagnostic coronary angiography might similarly impact occupational safety.

Methods

Stable patients referred for coronary angiography were prospectively enrolled. After obtaining vascular access, diagnostic catheters were manually advanced over a wire to the ascending aorta. All subsequent catheter movements were performed robotically. The primary endpoint was procedural success, defined as robotic completion of coronary angiography without conversion to a manual procedure and the absence of procedural major adverse cardiovascular events (MACE—cardiac death, cardiac arrest, or stroke) and major angiographic complications (coronary/aortic dissection or embolization). The primary hypothesis was that the observed rate of the primary endpoint, evaluated at the completion of coronary angiography, would meet a pre‐specified performance goal of 74.5%.

Results

Among 46 consecutive patients (age 67 ± 12 years; 69.6% male), diagnostic coronary angiography was completed robotically in all cases without the need for manual conversion and without any MACE or major angiographic complications. Thus, procedural success was 100%, which was significantly higher than the pre‐specified performance goal (p < 0.001). Robotic coronary angiography was completed using 2 [2, 3] catheters per case with a median procedural time of 15 [11, 20] minutes.

Conclusions

Robotic diagnostic coronary angiography was performed with 100% procedural success and no observed complications. These results support the performance of future studies to further explore robotic coronary angiography.
Characterization of einkorn and durum wheat flours by GlutoPeak and evaluation of pasta quality made of various substitution ratios of einkorn
Authors: Kaplan Evlice Asuman
Published: May 2022

Background and Objectives

This study aimed to investigate the effect of the replacement of durum wheat (Ankara 98) with an increasing amount of einkorn (Siyez) (30%, 50%, 70%, and 100%) on the chemical, physicochemical, and rheological properties of flour as well as cooking and textural properties of pasta.

Findings

Einkorn had poor aggregation properties of gluten examined by the new instrument GlutoPeak. An increase in firmness was determined in cooked pasta samples produced by replacing semolina with an increasing amount of einkorn flour. Besides this, the lowest optimum cooking time, cooking loss, water absorption, and breaking strength values were obtained from the pasta produced with 100% einkorn wholemeal flour. Yellow pigment contents of flour and pasta increased with an increasing amount of einkorn flour; however, einkorn pasta had darker color.

Conclusion

Einkorn had poor rheological characteristics and darker pasta color; however, the einkorn blend used in the present study enables the partial replacement of wheat semolina in pasta with acceptable cooking quality and texture.

Significance and Novelty

Pasta samples produced from einkorn or einkorn–durum blends had acceptable cooking quality and textural characteristics but better nutritional value than the durum wheat pasta.
Transoral removal of a hilo‐parenchymal submandibular sialolith
Authors: Kataoka Yo‐Hei , Kojima Yoshihiro , Ishibashi Ruri , Nakao Yuji , Yamamura Koji , Takahashi Shotaro , Hashiba Takafumi , Matsue Takahito
Published: May 2022

In sialolithiasis, the lithiasis is often large and located at the junction of the middle and posterior third of the duct, in the hilum region. In such cases, transoral approach for submandibular lithiases (TASL) is a useful treatment of choice in patients with large submandibular stones that can be palpated bimanually.
Alpha‐L‐iduronidase deficiency: A novel mutation resulting in severe early presentation of Mucopolysaccharidosis type I and literature review of the molecular basis
Authors: Al Zaabi Nuha Nasser , Sirajum Muneera , Al‐Wawi Mohd Zaki , Al Suwaiji Mohammed
Published: May 2022

The IDUA gene (MIM 252800) provides instructions for producing alpha‐L‐iduronidase, which is essential for the breakdown of large sugar molecules called glycosaminoglycans (GAGs). Mutations in the IDUA gene have been found to cause Mucopolysaccharidosis type I (MPS I) (MIM 607014). This leads to the accumulation of GAGs within lysosomes causing many different organs and tissues to be dysfunctional. Deleted IDUA gene has not been reported in the literature, which showed to be associated with a severe phenotype in our proband case. We report a child from a consanguineous family who presented with severe cardiogenic shock attributed to dilated cardiomyopathy. He was also found to have hepatosplenomegaly, joint stiffness, hearing loss, corneal hazing, facial dysmorphism, and dilation of brain ventricles. Lysosomal storage disease particularly MPS I was suspected though it is considered to be an early atypical presentation. The diagnosis was achieved via gene mutation analysis which showed homozygous IDUA deletion of exon 9′ to 3′ in combination with a severe deficiency of alpha‐L‐iduronidase enzyme. A variant in the form of IDUA gene deletion may indicate an early severe phenotypic presentation of MPS I. Establishment of the diagnosis permits genetic counseling, prevents patients from undergoing unhelpful diagnostic procedures, and allows for accurate prognosis.
Synthesis and Biological Evaluation of Flavonoid‐Cinnamic Acid Amide Hybrids with Distinct Activity against Neurodegeneration in Vitro and in Vivo
Authors: Hofmann Julian , Spatz Philipp , Walther Rasmus , Gutmann Marcus , Maurice Tangui , Decker Michael
Published: May 2022

Flavonoids are polyphenolic natural products and have shown significant potential as disease‐modifying agents against neurodegenerative disorders like Alzheimer's disease (AD), with activities even in vivo. Hybridization of the natural products taxifolin and silibinin with cinnamic acid led to an overadditive effect of these compounds in several phenotypic screening assays related to neurodegeneration and AD. Therefore, we have exchanged the flavonoid part of the hybrids with different flavonoids, which show higher efficacy than taxifolin or silibinin, to improve the activity of the respective hybrids. Chemical connection between the flavonoid and cinnamic acid was realized by an amide instead of a labile ester bond to improve stability towards hydrolysis. To investigate the influence of a double bond at the C‐ring of the flavonoid, the dehydro analogues of the respective hybrids were also synthesized. All compounds obtained show neuroprotection against oxytosis, ferroptosis and ATP‐depletion, respectively, in the murine hippocampal cell line HT22. Interestingly, the taxifolin and the quercetin derivatives are the most active compounds, whereby the quercetin derivate shows even more pronounced activity than the taxifolin one in all assays applied. As aimed for, no hydrolysis product was found in cellular uptake experiments after 4 h whereas different metabolites were detected. Furthermore, the quercetin‐cinnamic acid amide showed pronounced activity in an in vivo AD mouse model at a remarkably low dose of 0.3 mg/kg.
Improvement of Visible‐Light H2 Evolution Activity of Pb2Ti2O5.4F1.2 Photocatalyst by Coloading of Rh and Pd Cocatalysts
Authors: Aihara Kenta , Kato Kosaku , Uchiyama Tomoki , Yasuda Shuhei , Yokoi Toshiyuki , Yamakata Akira , Uchimoto Yoshiharu , Maeda Kazuhiko
Published: May 2022

Pb2Ti2O5.4F1.2 modified with various metal cocatalysts was studied as a photocatalyst for visible‐light H2 evolution. Although unmodified Pb2Ti2O5.4F1.2 showed negligible activity, modification of its surface with Rh led to the best observed promotional effect among the Pb2Ti2O5.4F1.2 samples modified with a single metal cocatalyst. The H2 evolution activity was further enhanced by coloading with Pd; the Rh−Pd/Pb2Ti2O5.4F1.2 photocatalyst showed 3.2 times greater activity than the previously reported Pt/Pb2Ti2O5.4F1.2. X‐ray absorption fine‐structure spectroscopy, photoelectrochemical, and transient absorption spectroscopy measurements indicated that the coloaded Rh and Pd species, which were partially alloyed on the Pb2Ti2O5.4F1.2 surface, improved the electron‐capturing ability, thereby explaining the high activity of the coloaded Rh−Pd/Pb2Ti2O5.4F1.2 catalyst toward H2 evolution.
Likelihood identifiability and parameter estimation with nonignorable missing data
Authors: Zheng Siming , Zhang Juan , Zhou Yong
Published: May 2022

We identify sufficient conditions to resolve the identification problem under nonignorable missingness, especially the identifiability of the observed likelihood when some of the covariate values are missing not at random, or, simultaneously, the response is also missing not at random. It is more difficult to tackle these cases than the nonignorable nonresponse case, and, to the best of our knowledge, the simultaneously missing case has never been discussed before. Under these conditions, we propose some parameter estimation methods. As an illustration, when some of the covariate values are missing not at random, we adopt a semiparametric logistic model with a tilting parameter to model the missingness mechanism and use an imputed estimating equation based on the generalized method of moments to estimate the parameters of interest and the tilting parameter simultaneously. This approach avoids the requirement for other independent surveys or a validation sample to estimate the unknown tilting parameter. The asymptotic properties of our proposed estimators are derived, and the proofs can be modified to show that our methods of estimation, which are based on inverse probability weighting, augmented inverse probability weighting, and estimating equation projection, have the same asymptotic efficiency when the tilting parameter is either known or unknown but estimated by some other method. In simulation studies, we compare our methods with various alternative approaches and find that our methods are more robust and effective.
Influence of Ion Specificity and Concentration on the Conformational Transition of Intrinsically Disordered Sheep Prion Peptide
Authors: Singh Omkar , Kumar Das Bratin , Chakraborty Debashree
Published: May 2022

The structural sensitivity of the intrinsically disordered proteins with the ions has been observed experimentally; however, it is still unclear how the presence of different metal ions affects structural stability. We performed an atomistic molecular dynamics simulation of sheep prion peptide (142–167) in presence of different monovalent, divalent ions at various concentrations to find out the effect of the size, charge, and ionic concentration on the structure of the peptide. It is found that Li+ ions have a higher survival probability compared to Na+, K+, and Mg2+ affecting the solvation structure of the protein leading to the alpha‐helix structure. At high concentration, due to the increase in the ion‐solvent and counter‐ion interactions, the effect of the ions is screened on the surface of the protein and hence no ion specificity is observed. This study demonstrates how ions can be used to regulate the protein structure and function that can help in designing drugs.
Effect of Chalcogen Incorporation and Rigidification on the Photovoltaic Properties of Simple Arylamine‐Based D‐π‐A Push–Pull Molecular Systems
Authors: Hossein Habibi Amir , Josse Pierre , Marqués Pablo Simón , Blanchard Philippe , Cabanetos Clément
Published: May 2022

Four D‐π‐A push–pull derivatives either based on a diphenylmethylamine or a 9‐methylcarbazole electron‐rich block (D), connected to a dicyanovinyl accepting moiety (A) through two different spacers (π), namely a thiophene or selenophene, were synthesized and characterized. These small and synthetically accessible molecules were indeed selected to rationalize the impact of both i) the rigidification of the arylamine part and ii) the nature of the π‐spacer constituting heteroatom on the optical, electrochemical, charge transport and therefore photovoltaic properties.
Increased amphiregulin expression by CD4+ T cells from individuals with asymptomatic Leishmania donovani infection
Authors: Singh Siddharth Sankar , Chauhan Shashi Bhushan , Ng Susanna SS , Corvino Dillon , de Labastida Rivera Fabian , Engel Jessica A , Waddell Nic , Mukhopadhay Pamela , Johnston Rebecca L , Koufariotis Lambros T , Nylen Susanne , Prakash Singh Om , Engwerda Christian R , Kumar Rajiv , Sundar Shyam
Published: May 2022

Objectives

There is an urgent need to be able to identify individuals with asymptomatic Leishmania donovani infection, so their risk of progressing to VL and transmitting parasites can be managed. This study examined transcriptional markers expressed by CD4+ T cells that could distinguish asymptomatic individuals from endemic controls and visceral leishmaniasis (VL) patients.

Methods

CD4+ T cells were isolated from individuals with asymptomatic L. donovani infection, endemic controls and VL patients. RNA was extracted and RNAseq employed to identify differentially expressed genes. The expression of one gene and its protein product during asymptomatic infection were evaluated.

Results

Amphiregulin (AREG) was identified as a distinguishing gene product in CD4+ T cells from individuals with asymptomatic L. donovani infection, compared to VL patients and healthy endemic control individuals. AREG levels in plasma and antigen‐stimulated whole‐blood assay cell culture supernatants were significantly elevated in asymptomatic individuals, compared to endemic controls and VL patients. Regulatory T (Treg) cells were identified as an important source of AREG amongst CD4+ T‐cell subsets in asymptomatic individuals.

Conclusion

Increased Treg cell AREG expression was identified in individuals with asymptomatic L. donovani infection, suggesting the presence of an ongoing inflammatory response in these individuals required for controlling infection and that AREG may play an important role in preventing inflammation‐induced tissue damage and subsequent disease in asymptomatic individuals.
Accounting for the genetic load in assisted reproductive technology
Authors: van Oosterhout Cock , Marcu Daniel , Immler Simone
Published: May 2022

The genetic load in the human genome has important ramifications for assisted reproductive technology (ART), human reproduction and fertility more generally. Here, we discuss these topics in the light of evolutionary genetic theory, the technological revolution in ART and the advances in the fields of genomics and bioinformatics.
Planning bus networks by exploiting GPS trajectories collected by IoT‐enabled vehicles
Authors: Zhang Xiaomei , Chen Peng , Tang Liangyao , Xia Yunni , Li Jianqi , Jiang Ning , Xie Hong , Xia Qing , Wu Lei
Published: May 2022

GPS traces collected by IoT‐enabled vehicle sensors are highly informative and exploitable in the area of human mobility analysis and traffic control. In this work, we focus on generating effective bus routes and networks by analyzing and exploiting the Taxi GPS trajectories. Specifically, we develop a novel framework for yielding potential bus stations by analyzing passenger boarding and getting spots collected by IoT‐enabled vehicle sensors, a novel ant‐colony‐based heuristic for generating serving routes and further for yielding the bus network. For the model validation purpose, we perform extensive simulations upon a dataset of metropolitan traveling traces and illustrate that our approach definitely beats state‐of‐the‐art ones in terms of the number of people served.