bluuebunny/crossref_metadata_2025 huggingface dataset:
CH to CN Bonds via Radical‐Mediated Chemistry
Authors: Ward Robert M. , Schomaker Jennifer M.
Published: July 2022

New methods for the formation of CN bonds to prepare compounds with wide‐ranging applications in medicinal, materials, and synthetic chemistry are continually evolving. Early methods for CN bond formation required prefunctionalized substrates, such as halides, pseudohalides, and carbonyl compounds. These approaches often resulted in increased step count, decreased atom economy, and limitations in functional group compatibility. To address these shortcomings, the direct functionalization of CH bonds has emerged as an attractive strategy. The ability to achieve direct exchange of a hydrogen atom for a nitrogen in the later stages of a synthesis is an especially powerful tool in a synthetic chemist's toolbox. Approaches to direct amination can be subdivided into those containing open‐shell intermediates, which will be described in this article, and concerted pathways, which will not be covered. Topics that will be discussed include strategies for C(sp
3
)H amination involving both inter‐ and intramolecular 1,
n
‐hydrogen atom transfer (HAT), intermolecular C(sp
3
)H amination, C(sp
3
)H amination via nitrene transfer, and net C(sp
2
)H amination. Traditional examples as well as the more recent strategies that utilize photo‐ and electrochemical methods are presented. Selected examples from the literature will be presented, but previous reviews and articles are referenced here for further reading.
Assessing the practicality of using a single knowledge‐based planning model for multiple linac vendors
Authors: Douglas Raphael J. , Olanrewaju Adenike , Zhang Lifei , Beadle Beth M. , Court Laurence E.
Published: July 2022

Purpose

Knowledge‐based planning (KBP) has been shown to be an effective tool in quality control for intensity‐modulated radiation therapy treatment planning and generating high‐quality plans. Previous studies have evaluated its ability to create consistent plans across institutions and between planners within the same institution as well as its use as teaching tool for inexperienced planners. This study evaluates whether planning quality is consistent when using a KBP model to plan across different treatment machines.

Materials and methods

This study used a RapidPlan model (Varian Medical Systems) provided by the vendor, to which we added additional planning objectives, maximum dose limits, and planning structures, such that a clinically acceptable plan is achieved in a single optimization. This model was used to generate and optimize volumetric‐modulated arc therapy plans for a cohort of 50 patients treated for head‐neck cancer. Plans were generated using the following treatment machines: Varian 2100, Elekta Versa HD, and Varian Halcyon. A noninferiority testing methodology was used to evaluate the hypothesis that normal and target metrics in our autoplans were no worse than a set of clinically‐acceptable baseline plans by a margin of 1.8 Gy or 3% dose‐volume. The quality of these plans were also compared through the use of common clinical dose‐volume histogram criteria.

Results

The Versa HD met our noninferiority criteria for 23 of 34 normal and target metrics; while the Halcyon and Varian 2100 machines met our criteria for 24 of 34 and 26 of 34 metrics, respectively. The experimental plans tended to have less volume coverage for prescription dose planning target volume and larger hotspot volumes. However, comparable plans were generated across different treatment machines.

Conclusions

These results support the use of a head‐neck RapidPlan models in centralized planning workflows that support clinics with different linac models/vendors, although some fine‐tuning for targets may be necessary.
Fantastical Monsters: The Persistent Memory of Machines
Authors: Betsky Aaron
Published: July 2022

Virginia Tech School of Architecture and Design Professor and renowned curator, critic and writer Aaron Betsky investigates the machinic architectural worlds of architect Bryan Cantley. Professor of Design Theory at California State University, Fullerton, Cantley has been developing a considerable and starkly individual body of work since his MArch at the University of California, Los Angeles in the early 1990s.
Urban Cartographies: Drawing Seen Through Bacon's Painting
Authors: Salter Peter
Published: July 2022

Art, architecture and urbanism practice Metis was founded by Professor Mark Dorrian, Forbes Chair in Architecture, and Adrian Hawker, MArch Programme Director, at the University of Edinburgh. Metis has a long history of proposing extraordinary architectures, whether in building form or as interventions in existing spaces. Architect and academic Peter Salter uses the lens of Francis Bacon's painting to view their creative tactics.
World‐Shaping: Choreographies of Mapping and Construction
Authors: Wilson Robin
Published: July 2022

The projection and tailoring of architectural space is a deeply personal occupation intertwined with a designer's history, education and geographical roots. British architect Shaun Murray has a very individual way of representing and positing situations and spaces, which he communicates through his multilayered airbrushed drawings. Historian, theorist and critic Robin Wilson analyses his influences and aspirations.
Thick Fields and Aberrant Transmutations
Authors: Smith Chris L
Published: July 2022

Compelled to creatively mark the death of his good friend, Neil Spiller has memorialised the renowned graphic designer Vaughan Oliver in an augmented reality roof garden on top of the Longhouse, the centrepiece of his long‐running ‘Communicating Vessels’ drawing series. Here, architectural theory professor at the University of Sydney Chris L Smith explores the work, ploughs its fields, and surveys its sky.
Self‐Propelled Catalytically Powered Dual‐Engine Magnetic Nanobots for Rapid and Highly Efficient Capture of Circulating Fetal Trophoblasts
Authors: Wavhale Ravindra D. , Dhobale Kshama D. , Patil Shraddha , Chate Govind P. , Tawade Bhausaheb V. , Patil Yuvraj N. , Banerjee Shashwat S.
Published: July 2022

Here, chemically powered and magnetically guided janus magneto‐fluorescent dual‐engine nanobots (MFDEN) that harvest their energy from the reactions with two different fuels are reported. The Mg‐Fe3O4 Janus nanobots prepared by depositing Fe3O4 hemispherical layer on Mg nanoparticles are propelled efficiently by the thrust of oxygen bubble generated from the reactions of Fe3O4 in H2O2 media, and by hydrogen bubble produced at the partial Mg opening in aqueous media. High speeds and long lifetimes are achieved in complex biological media with H2O2 or with NaHCO3, respectively. For the first time, this study demonstrates the utility of nanobots for efficient isolation of trophoblastic cells from blood. Considering the extreme rarity of these cells in blood, efficient technique that enriches sufficient cells rapidly and with specificity is desired. The nanobots exhibit excellent capture efficiency of almost 100%, both in serum and whole blood for trophoblastic Be‐Wo cells. Furthermore, the high capture efficiency is achieved in 5 min. Feasibility of obtaining an isolated cell based diagnosis from whole blood is demonstrated. Although determining the exact sensitivity and specificity will require more data, this study supports the potential of the multiple fuel‐powered nanorobots for clinical translation of circulating fetal cell based non‐invasive prenatal testing.
Supramolecular Gel Lubricants with Excellent Lubricity and Load‐Carrying Performances Act Synergistically via Two Layers of Tribofilm
Authors: Xie Ao , Bai Yanyan , Xu Hao‐Zhe , Dong Rui , Zhang Jiaying , Yu Qiangliang , Lv Wenquan , Zhang Ming , Liang Yijing , Wang Xin‐Gang , Cai Meirong , Zhou Feng
Published: July 2022

Lubrication failure under heavy load condition due to the limited carrying capacity of base lubricants usually results in catastrophic failure of mechanical systems. In this work, a class of perfluorinated gel lubricants (PFGs) is prepared, retaining excellent lubricity and load‐carrying performances under high load. Self‐assembly mechanism confirmed by molecular dynamics simulation indicates that the gelators in PFGs self‐assemble into a 3D network structure through intermolecular hydrogen bonds. The confinement effect of gelator self‐assembly in the base oil contributes to avoiding lubrication failure and environmental pollution caused by base oil creeping and leakage. Simple synthesis, creep recovery, and high sol–gel phase transition temperatures confer more benefits for PFGs applications. Moreover, X‐ray photoelectron spectroscopy and transmission electron microscopy techniques are employed to investigate the lubrication mechanism of PFGs, revealing that lubricants can interact with the friction interface to form two layers of tribofilm which are formed by adsorption and tribochemical reaction. PFGs provide an eco‐friendly solution for lubricating under heavy load condition.
Intercalation of Small Organic Molecules into Ti3C2Tx MXene Cathodes for Flexible High‐Volume‐Capacitance Zn‐Ion Microsupercapacitor
Authors: Liu Weijia , Li La , Hu Chuqiao , Chen Di , Shen Guozhen
Published: July 2022

The delamination of 2D Ti3C2Tx MXene endows the injection of various ions and small organic molecules into its layers, thus leading to a tunable distance between layers and adjustable electrochemical properties. A suitable selection of intercalators needs to be considered according to the relevant metal‐ion‐based energy storage device because of the different radii of metal ions such as Li+, Na+, Mg2+ Zn2+, etc. Herein, the intercalation of N,N‐dimethylacetamide (DMAC), acetonitrile (ACN), dimethyl sulfoxide (DMSO), LiCl (H2O) into Ti3C2Tx cathodes and their electrochemical performance comparisons by fabricating Zn‐ion microsupercapacitors (MSCs) is reported. Studies found that an increased calculated interlayer space of 3.42, 7.47, 7.79, 8.3 Å is obtained for the H2O, DMSO, ACN, DMAC intercalated Ti3C2Tx cathodes, and a decreased calculated binding energy of −0.03, −0.78, −1.91, and −3.06 eV is obtained for the Ti3C2Tx‐H2O, Ti3C2Tx‐DMSO, Ti3C2Tx‐ACN, and Ti3C2Tx‐DMAC, respectively. The highest interlayer space, lowest binding energy, and amide groups make the DMAC intercalated Ti3C2Tx‐based MSC exhibit volumetric capacitance of 1873 F cm−3 at a scan rate of 5 mV s−1, much higher than 1103 F cm−3 for Ti3C2Tx‐H2O, 1313 F cm−3 for Ti3C2Tx‐ACN, 544 F cm−3 for Ti3C2Tx‐DMSO. The superior flexibility that results in invariable capacitance under 5000 bending cycles, together with the lighting test of the fabricated MSC, demonstrates its application in the wearable integrated system.
Inkjet Printing of Quasi‐2D Perovskite Layers with Optimized Drying Protocol for Efficient Solar Cells
Authors: Wilk Barbara , Sahayaraj Sylvester , Ziółek Marcin , Babu Vivek , Kudrawiec Robert , Wojciechowski Konrad
Published: July 2022

Metal halide perovskites of reduced dimensionality constitute an interesting subcategory of the perovskite semiconductor family, which attract a lot of attention, primarily due to their excellent moisture resistance and peculiar optoelectronic properties. Specifically, quasi‐2D materials of the Ruddlesden–Popper (RP) type, are intensely investigated as photoactive layers in perovskite solar cells. Here, a scalable deposition of quasi‐2D perovskite thin films, with a nominal composition of 4F‐PEA2MA4Pb5I16 (4‐FPEA+‐4‐fluoro‐phenethylammonium, applied as a spacer cation), using an inkjet printing technique, is developed. An optimized precursor formulation, and appropriate post‐printing treatment, which enable good control over nucleation and crystal growth steps, result in highly crystalline and uniform perovskite layers. Particularly, vacuum with nitrogen flushing provides an optimal drying treatment, which produces a more uniform distribution of low dimensional phases, and a high level of vertical (out‐of‐plane) alignment, which is beneficial for charge carrier transport. Solar cells reaching 13% of power conversion efficiency for the rigid, and 10.6% for the flexible, large area (1 cm2) devices are presented.
Imine Azaenolates: Synthesis, Reactivity, and Outlook
Authors: St John‐Campbell Sahra , Sheppard Tom D.
Published: July 2022

Azaenolates are, quite simply, the aza variant of enolates. Compared to their oxygen counterparts, additional control of the reactivity of azaenolates can be achieved by altering the substituent on the nitrogen atom as well as the metal counterion. Since the seminal examples reported in the early 1960s, azaenolates of various metals have been shown to react with a diverse set of electrophilic partners, including challenging electrophiles such as alkyl fluorides, epoxides, and oxetanes. This review describes in detail the current state of the art of the chemistry of azaenolates derived from imines, with a particular focus on the comparison of the reactivity exhibited with different metal counterions.

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Foldable and Recyclable Iontronic Cellulose Nanopaper for Low‐Power Paper Electronics
Authors: Cunha Inês , Ferreira Sofia Henriques , Martins Jorge , Fortunato Elvira , Gaspar Diana , Martins Rodrigo , Pereira Luís
Published: July 2022

An increase in the demand for the next generation of “Internet‐of‐Things” (IoT) has motivated efforts to develop flexible and affordable smart electronic systems, in line with sustainable development and carbon neutrality. Cellulose holds the potential to fulfil such demands as a low‐cost green material due to its abundant and renewable nature and tunable properties. Here, a cellulose‐based ionic conductive substrate compatible with printing techniques that combines the mechanical robustness, thermal resistance and surface smoothness of cellulose nanofibrils nanopaper with the high capacitance of a regenerated cellulose hydrogel electrolyte, is reported. Fully screen‐printed electrolyte‐gated transistors and universal logic gates are demonstrated using the engineered ionic conductive nanopaper and zinc oxide nanoplates as the semiconductor layer. The devices exhibit low‐voltage operation (<3 V), and remarkable mechanical endurance under outward folding due to the combination of the robustness of the nanopaper and the compliance of the semiconductor layer provided by the ZnO nanoplates. The printed devices and the ion‐conductive nanopaper can be efficiently recycled to fabricate new devices, which is compatible with the circular economy concept.
A Conductive Molecular Semiconductor Composite with Over 160 °C Glass Transition Temperature for Heat‐Resistant Perovskite Solar Cells
Authors: Xie Xinrui , He Lifei , Wei Yuefang , Li Tianyu , Yuan Yi , Zhang Jing , Wang Peng
Published: July 2022

Under long‐term thermal stress, the decomposition of organic‐inorganic hybrid perovskite is a big challenge to realize stable and efficient perovskite solar cells (PSCs). Thereby, it is of pivotal importance to engineer an organic hole transport layer, which is featured not only by an excellent hole conduction but also by a high glass transition temperature. Here, a solution‐processible molecular semiconductor (T5H‐EP‐BMCA) is reported. The air‐doped composite of T5H‐EP‐BMCA presents a hole density of 6.5 × 1017 cm–3, a space‐charge‐limited current hole mobility of 5.1 × 10–4 cm2 V–1 s–1, and a direct‐current electrical conductivity of 30.6 µS cm–1. Moreover, the conductive composite owns a high glass transition temperature of 165 °C, a heat‐resistant morphology, and low gas permeability coefficients. These joint attributes allow for the fabrication of 21.0%‐efficiency, 85 °C‐durable PSC by controlling the thermal decomposition of perovskite.
Ruthenium‐catalyzed C−H Functionalization/Annulation ofN‐Aryl Indazoles/Phthalazines with Sulfoxonium Ylides to access Tetracyclic‐fused Cinnolines
Authors: Pan Changduo , Yuan Cheng , Yu Jin‐Tao
Published: July 2022

A ruthenium‐catalyzed cascade C−H functionalization/intramolecular annulation ofN‐phenylindazoles with sulfoxonium ylides was developed for the synthesis of indazolo[1,2‐a]cinnolinones. This transformation features with C−H/N−H functionalization inone pot, the utilization of cost‐effective ruthenium catalyst, wide substrate scope and good functional group tolerance. Moreover, the reaction of 2‐arylphthalazine‐1,4‐diones with sulfoxonium ylides led to phthalazino[2,3‐a]cinnolindiones under standard conditions.
Longitudinal changes in brain oxygen extraction fraction (OEF) in older adults: Relationship to markers of vascular and Alzheimer's pathology
Authors: Lin Zixuan , Lim Chantelle , Jiang Dengrong , Soldan Anja , Pettigrew Corinne , Oishi Kumiko , Zhu Yuxin , Moghekar Abhay , Liu Peiying , Albert Marilyn , Lu Hanzhang
Published: July 2022

Introduction

Oxygen extraction fraction (OEF) reflects the balance between oxygen delivery and consumption. We longitudinally measured OEF in older adults to examine the relationship with markers of Alzheimer's disease (AD) and vascular pathology.

Methods

One hundred thirty‐seven participants were studied at two time‐points at an interval of 2.16 years. OEF was measured using T2‐relaxation‐under‐spin‐tagging (TRUST) magnetic resonance imaging (MRI). The association between OEF and vascular risks, white matter hyperintensities (WMH), cerebrospinal fluid (CSF) measures of amyloid beta (Aβ), total tau (t‐tau), and phosphorylated tau 181 (p‐tau181) was examined.

Results

OEF increased from baseline to follow‐up. The increase in OEF was more prominent in individuals with high vascular risks compared to those with low vascular risks, and was associated with progression of vascular risks and the growth in WMH volume. OEF change was not related to CSF markers of AD pathology or their progression.

Discussion

Longitudinal OEF change in older adults is primarily related to vascular pathology.
Hypervalent Chalcogenonium⋅⋅⋅π Bonding Catalysis
Authors: Zhang Qingyu , Chan Yung‐Yin , Zhang Muyin , Yeung Ying‐Yeung , Ke Zhihai
Published: July 2022

A proof‐of‐concept study of hypervalent chalcogenonium⋅⋅⋅π bonding catalysis was performed. A new catalytic strategy using 1,2‐oxaselenolium salts as chalcogen bond donors and alkenes as chalcogen bond acceptors is described. The feasibility of this concept is demonstrated by the use of trisubstituted selenonium salts in the metal‐free catalytic hydrofunctionalization and polymerization of alkenes via unconventional seleniranium ion‐like intermediates. The results indicate that counter anions have a significant effect on the catalysis based on hypervalent chalcogenonium⋅⋅⋅π bonding interactions.
Structure‐Based Demystification of Radical Catalysis by a Coenzyme B12 Dependent Enzyme—Crystallographic Study of Glutamate Mutase with Cofactor Homologues
Authors: Gruber Karl , Csitkovits Vanessa , Łyskowski Andrzej , Kratky Christoph , Kräutler Bernhard
Published: July 2022

Catalysis by radical enzymes dependent on coenzyme B12 (AdoCbl) relies on the reactive primary 5′‐deoxy‐5′adenosyl radical, which originates from reversible Co−C bond homolysis of AdoCbl. This bond homolysis is accelerated roughly 1012‐fold upon binding the enzyme substrate. The structural basis for this activation is still strikingly enigmatic. As revealed here, a displaced firm adenosine binding cavity in substrate‐loaded glutamate mutase (GM) causes a structural misfit for intact AdoCbl that is relieved by the homolytic Co−C bond cleavage. Strategically interacting adjacent adenosine‐ and substrate‐binding protein cavities provide a tight caged radical reaction space, controlling the entire radical path. The GM active site is perfectly structured for promoting radical catalysis, including “negative catalysis”, a paradigm for AdoCbl‐dependent mutases.
A General and Efficient Solution to Monofluoroalkylation: Divergent Synthesis of Aliphatic Monofluorides with Modular Synthetic Scaffolds
Authors: Wu Bing‐Bing , Xu Jie , Gao Qian , Bian Kang‐Jie , Liu Guo‐Kai , Wang Xi‐Sheng
Published: July 2022

Monofluoroalkanes are important in many pharmaceuticals, agrochemicals and functional materials. However, the lack of easily available and transformable monofluoroalkylating reagents that facilitate a broad array of transformations has hampered the application of monofluoroalkylation. Herein, we report a general and efficient method of preparing diverse aliphatic monofluorides with monofluoroalkyl triflate as the synthetic scaffold. Using both nickel‐catalyzed hydromonofluoroalkylation of unactivated alkenes and copper‐catalyzed C−C bond formation, the general diversification of the monofluoroalkylating scaffold has been exhibited. The broad utility of this monofluoroalkylating reagent is shown by concise conversion into various conventional fluoroalkylating reagents and construction of monofluoro‐alkoxy, ‐alkylamino motifs with commercially available heteroatom‐based coupling partners.
[NN]‐Chelate nickel complexes with Schiff base ligands: Synthesis, structure and catalytic activity in green amidation reaction
Authors: Guo Wen , Liu Zhen‐Jiang , Wu Fanhong , Luo Yu‐Zhou , Yao Zi‐Jian
Published: July 2022

A series of N,N‐coordinate nickel (II) complexes with Schiff base ligands have been synthesized. All N,N‐coordinate nickel (II) complexes 1–4 were well characterized by IR and elemental analysis. Molecular structure of complex 1 was further characterized by single crystal X‐ray diffraction analysis. All air and moisture stable nickel complexes showed efficient catalytic activity for the amidation reaction of a widely range of amides and primary alcohols. N‐alkylated amides were given in good to excellent yields with liberating water as the sole byproduct. A variety types of functional groups tolerated well in such reaction condition. In addition, control experiments were carried out to understand this Ni‐catalysis protocol.
Association of 18F‐Fluorodeoxyglucose–Positron Emission Tomography Activity With Angiographic Progression of Disease in Large Vessel Vasculitis
Authors: Quinn Kaitlin A. , Ahlman Mark A. , Alessi Hugh D. , LaValley Michael P. , Neogi Tuhina , Marko Jamie , Novakovich Elaine , Grayson Peter C.
Published: July 2022

Objective

To assess whether vascular activity seen on 18F‐fluorodeoxyglucose–positron emission tomography (FDG‐PET) scan is associated with angiographic change in large vessel vasculitis (LVV).

Methods

Patients with LVV were recruited into a prospective cohort. All patients underwent magnetic resonance angiography or computed tomography angiography and FDG‐PET imaging. Follow‐up imaging using the same imaging modalities was obtained ≥6 months later per a standardized imaging protocol. Arterial damage, defined as stenosis, occlusion, or aneurysm, and corresponding FDG uptake were evaluated in 17 arterial territories. On follow‐up, development of new lesions was recorded, and existing lesions were characterized as improved, worsened, or unchanged.

Results

A total of 1,091 arterial territories from 70 patients with LVV (38 patients with Takayasu arteritis, 32 patients with giant cell arteritis) were evaluated. Over a median 1.6 years of follow‐up, new lesions developed only in 8 arterial territories in 5 patients with Takayasu arteritis. Arterial lesions improved in 16 territories and worsened in 6 territories. Most arterial territories that did not have vascular activity on FDG‐PET scan at baseline had no angiographic change over the follow‐up period (787 [99%] of 793). Few territories with baseline FDG‐PET activity had angiographic change over time (24 [8%] of 298), but of the territories that developed angiographic change, 80% had FDG‐PET activity at baseline. Within the same patient, an arterial territory with baseline FDG‐PET activity had significantly increased risk for angiographic change compared to a paired arterial territory without FDG‐PET activity (odds ratio 19.49 [95% confidence interval 2.44–156.02]; P < 0.01). Concomitant edema and wall thickening further increased risk for angiographic change.

Conclusion

Development of angiographic change was infrequent in this cohort of patients with LVV. A lack of baseline FDG‐PET activity was strongly associated with stable angiographic disease. In cases of angiographic progression, change was preceded by the presence of FDG‐PET activity.
Denver Water Ensures a Sustainable Future With Its Northwater Treatment Plant
Authors: Mukherjee Sananda , Geiger Lindsey
Published: July 2022

Key Takeaways

Denver Water's project to upgrade part of its water system involves building a new treatment plant, installing new pipeline, and redeveloping the existing treatment plant.

Good stewardship through commitment to protecting the environment, serving current and future populations, and exercising fiscal responsibility is woven into the Northwater Treatment Plant project.

The Envision sustainability assessment framework, along with pursuit of the Envision Gold Award, has helped Denver Water achieve its project objectives.
Politics of evidence: Think tanks and the Academies Act
Authors: Kauko Jaakko
Published: July 2022

Previous research has identified political ideology as central in the landmark Academies Act (2010). This article further analyses how politics of evidence played its part in the policy process by focusing on long‐term structural changes and preferences among policymakers. The article draws on policymaker interviews after the reform, a mapping of think tanks and a document analysis. The analysis shows that political–ideological preferences were derived from think tanks, and the Conservative manifesto built on skewed Swedish evidence in constructing an argument for the Act. The political choices morphed into fact‐based arguments in the policy process. While think tanks had some reservations, in the Whitehall bureaucracy the argument was reformulated as a rational deliberation. This was possible because of the long‐term change in the significance of think tanks, and how policymakers preferred politically informed opinions instead of research evidence. The conclusion argues that the evidence‐based policy emphasis is an attempt to depoliticise the scope for political arguments. The political dynamic thus results in structurally empowered and layered but depoliticising use of evidence.
LIBS‐ und Elektrolytwiderstands‐Untersuchungen – Bausteine einer vertieften Bauwerksdiagnose bei chloridbelasteten Stahlbetonbauteilen
Authors: Kapteina Gesa , Dauberschmidt Christoph , Vestner Stephan , Langer Christoph
Published: July 2022

Chloride in Stahlbetonbauteilen können zu einer schädigenden Lochkorrosion der Bewehrung führen, die von außen nicht unbedingt sichtbar ist. Um den Schädigungsgrad der Bauteile und das Schädigungspotenzial auch hinsichtlich der zu wählenden Instandsetzungsvariante möglichst zielgerichtet ermitteln zu können, werden neben den herkömmlichen Methoden der Bauwerksdiagnose auch zunehmend zwei weitere Untersuchungsmethoden angewandt: So können durch gezielte Untersuchungen mit LIBS (Laser induzierte Breakdown Spektroskopie) wertvolle zusätzliche Informationen zur Chloridverteilung innerhalb des Bauwerks generiert werden. Mittels Bestimmung des Elektrolytwiderstands können Bauteile hinsichtlich des Wassergehalts und der Dichtigkeit und damit das Schädigungspotenzial beurteilt werden. Die Anwendungen beider Verfahren bei der Bauwerksdiagnose werden nachfolgend vorgestellt. Abschließend wird dargestellt, wie in Abhängigkeit von den später durchgeführten Instandsetzungsverfahren nach der Technischen Regel „Instandhaltung von Betonbauwerken“ (kurz: TR‐IH) des DIBt unterschiedliche Untersuchungsmethoden unterschiedliche Wichtigkeiten und Wertigkeiten aufweisen. Dies soll in der Praxis eine auf das Instandsetzungsverfahren zugeschnittene Bauwerksdiagnose ermöglichen.
Phage‐free production of artificial ssDNA with Escherichia coli
Authors: Behler Karl L. , Honemann Maximilian N. , Silva‐Santos Ana R. , Dietz Hendrik , Weuster‐Botz Dirk
Published: July 2022

Artificial single‐stranded DNA (ssDNA) with user‐defined sequences and lengths up to the kilobase range is increasingly needed in mass quantities to realize the potential of emerging technologies such as genome editing and DNA origami. However, currently available biotechnological approaches for mass‐producing ssDNA require dedicated, and thus costly, fermentation infrastructure, because of the risk of cross‐contaminating manufacturer plants with self‐replicating phages. Here we overcome this problem with an efficient, scalable, and cross‐contamination‐free method for the phage‐free biotechnological production of artificial ssDNA with Escherichia coli. Our system utilizes a designed phagemid and an optimized helper plasmid. The phagemid encodes one gene of the M13 phage genome and a freely chosen custom target sequence, while the helper plasmid encodes the other genes of the M13 phage. The phagemid particles produced with this method are not capable of self‐replication in the absence of the helper plasmid. This enables cross‐contamination‐free biotechnological production of ssDNA at any contract manufacturer. Furthermore, we optimized the process parameters to reduce by‐products and increased the maximal product concentration up to 83 mg L−1 of ssDNA in a stirred‐tank bioreactor, thus realizing up to a 40‐fold increase in maximal product concentration over previous scalable phage‐free ssDNA production methods.
Clinical effect of flunarizine combined with duloxetine in the treatment of chronic migraine comorbidity of depression and anxiety disorder
Authors: Zhu Junliang , Chen Jianhuang , Zhang Kaixue
Published: July 2022

Background

Migraine is common in primary headaches, and with the development of social economy and the increase in living pressure, the prevalence of migraine has an upward trend.

Objective

To observe the clinical effect of flunarizine combined with duloxetine in the treatment of chronic migraine with comorbid depression and anxiety disorders and to provide a reference for clinical treatment.

Methods

A total of 118 patients with chronic migraine complicated with depression and anxiety disorder admitted to our hospital from June 2018 to August 2020 were selected and divided into two groups according to treatment methods, 59 cases in each group. The control group was treated with flunarizine combined with loxoprofen sodium, and the observation group was treated with flunarizine combined with duloxetine. The changes of electroneurophysiological indexes, tumor necrosis factor‐α (TNF‐α), interleukin‐6 (IL‐6), high sensitivity‐C reactive protein (hs‐CRP), Hamilton depression scale (HAMD) score, and Hamilton anxiety scale (HAMA) score before and after treatment in the two groups were recorded, and the total effective rate of clinical treatment in the two groups was counted.

Results

After treatment, TNF‐α, IL‐6, and hs‐CRP in the two groups decreased gradually (p < .05). Further comparison between groups showed that TNF‐α, IL‐6, and hs‐CRP in the observation group were lower than those in the control group (p < .05). After treatment, the HAMD score and the HAMA score of the two groups decreased gradually (p < .05). Further comparison between the two groups showed that HAMD score and HAMA score of the observation group were lower than those of the control group (p < .05).

Conclusion

Flunarizine combined with duloxetine in the treatment of chronic migraine with depression and anxiety disorder can effectively improve neuroelectrophysiological indexes, reduce inflammation, and reduce depression and anxiety.
Theoretical Perspectives in Organocatalysis
Authors: Melnyk Nika , Iribarren Iñigo , Mates‐Torres Eric , Trujillo Cristina
Published: July 2022

It is clear that the field of organocatalysis is continuously expanding during the last decades. With increasing computational capacity and new techniques, computational methods have provided a more economic approach to explore different chemical systems. This review offers a broad yet concise overview of current state‐of‐the‐art studies that have employed novel strategies for catalyst design. The evolution of the all different theoretical approaches most commonly used within organocatalysis is discussed, from the traditional approach, manual‐driven, to the most recent one, machine‐driven.
Universal Trends between Acid Dissociation Constants in Protic and Aprotic Solvents
Authors: Busch Michael , Ahlberg Elisabet , Laasonen Kari
Published: July 2022

pKa values in non‐aqueous solvents are of critical importance in many areas of chemistry. Our knowledge is, despite their relevance, still limited to the most fundamental properties and few pKa values in the most common solvents. Taking advantage of a recently introduced computationally efficient procedure we computed the pKa values of 182 compounds in 21 solvents. This data set is used to establish for the first time universal trends between all solvents. Our computations indicate, that the total charge of the molecule and the charge of the acidic group combined with the Kamlet‐Taft solvatochromic parameters are sufficient to predict pKa values with at least semi‐ quantitative accuracy. We find, that neutral acids such as alcohols are strongly affected by the solvent properties. This is contrasted by cationic acids like ammonium ions whose pKa is often almost completely independent from the choice of solvent.
Molecular Insights of Non‐fused Ring Acceptors for High‐Performance Non‐fullerene Organic Solar Cells
Authors: Li Yibin , Yu Jiangsheng , Zhou Yinhua , Li Zhong'an
Published: July 2022

Non‐fullerene acceptors with fused‐ring structures have rapidly improved the performance of organic solar cells over the past five years, but they still suffer from synthetic complexity and thus high material costs, one of the major obstacles of hindering their commercialization process. The construction of non‐fused ring acceptors (NFRAs) has recently been regarded as a feasible solution due to their facile synthesis and satisfactory device performances. Thus in this concept, we highlight the important progress of NFRAs in recent years, and discuss the key relationship between molecular design strategies and device performance. Finally, we provide some potential molecular insights for the future design of high‐performance NFRAs.
Clinical activity of checkpoint inhibitors in angiosarcoma: A retrospective cohort study
Authors: Ravi Vinod , Subramaniam Aparna , Zheng Jing , Amini Behrang , Trinh Van A. , Joseph Jocelyn , Mennel Robert G. , Bishop Andrew J. , Sturgis Erich M. , Goepfert Ryan P. , Yalamanchili Sudha , Botello Gilberto , Stephen Bettzy , Piha‐Paul Sarina A. , Patel Anisha B. , Lazar Alexander J. , Conley Anthony P. , Benjamin Robert S. , Patel Shreyaskumar R. , Futreal Phillip A. , Somaiah Neeta , Naing Aung
Published: July 2022

Background

Systemic treatments for angiosarcoma remains an area of unmet clinical need. The authors conducted this retrospective study to assess the clinical activity of checkpoint inhibitors in patients with angiosarcoma. The primary objective was to assess the objective response rate, and the secondary objective was to assess the progression‐free and overall survival durations and disease control rate.

Methods

Patient data were obtained using The University of Texas MD Anderson Cancer Center Tumor Registry database. The final study population was refined to only include patients who had undergone pembrolizumab monotherapy. The objective response rate was evaluated using RECIST/irRECIST version 1.1. Progression‐free survival and overall survival were defined as the time from the initiation of immunotherapy to disease progression or recurrence, death, or last follow‐up and to death or last follow‐up, respectively.

Results

The final cohort comprised 25 patients. Most patients had metastatic disease (72%) and had undergone at least two lines of systemic therapy (80%) before starting pembrolizumab. The objective response rate was 18%, whereas the disease control rate was 59%. The median progression‐free survival duration was 6.2 months and was not significantly different between the cutaneous (4.7 months) and visceral angiosarcoma (6.2 months) groups (p = .42). The median overall survival duration was 72.6 months. Toxicities were recorded for eight patients, with fatigue, anemia, constipation, and rash being the most common.

Conclusions

Pembrolizumab shows durable clinical activity in angiosarcoma. These findings suggest that checkpoint inhibition as monotherapy or combination therapy is likely to have a high probability of success.© 2022 American Cancer Society.

Lay summary

This is the largest retrospective study to assess the clinical activity of checkpoint inhibitor monotherapy in angiosarcomas.

The study includes an adequate number of patients with visceral angiosarcoma that enabled to obtain meaningful clinical insights that were previously unavailable.

Our findings indicate an improvement in progression‐free survival with pembrolizumab that is comparable to other active agents in angiosarcoma.

Pembrolizumab monotherapy in angiosarcomas also has a favorable tolerability profile.

Our findings emphasize the need for prospective studies to evaluate the activity of pembrolizumab monotherapy and combination therapy.
Characteristics and outcomes of pediatric oncology patients at risk for guardians declining transfusion of blood components
Authors: Stevenson Jason , DeGroote Nicholas P. , Keller Frank , Brock Katharine E. , Bergsagel D. John , Miller Tamara P. , Cornwell Patricia , Fasano Ross , Chonat Satheesh , Castellino Sharon M.
Published: July 2022

Background

Transfusion of blood products is a necessary part of successful delivery of myelosuppressive regimens in pediatric cancer. There is a paucity of literature characterizing outcomes or management of pediatric patients with cancer when transfusion is declined.

Aims

The objective of this paper is to describe the clinical characteristics, care, and outcomes of patients with cancer at risk for declining transfusion.

Methods and Results

A retrospective cohort of patients aged 0–21 years with cancer managed at Children's Healthcare of Atlanta between 2006 and 2020 and with ICD‐9 codes indicating risk of “transfusion refusal” or Jehovah's witness (JW) religion was identified. Demographics, disease, and management were abstracted. Descriptive statistics were performed to examine associations with transfusion receipt. Among 35 eligible patients identified as at risk for declining transfusion, 89% had primary guardians who identified as JW, and 45.7% identified as Black, non‐Hispanic. Only 40% of guardians actively declined transfusion. Transfusion recipients had significantly lower hemoglobin (g/dl) and platelet counts (1000/μl) at initial presentation (9.6 vs. 11.9, p < .002 and 116.0 vs. 406.5, p = .001, respectively) and at nadir (5.9 vs. 8.7, p < .001 and ≤ 10 vs. 154, p < .001, respectively) than non‐recipients. Legal intervention was required in 36.4% of those who ultimately received a transfusion.

Conclusion

Among pediatric cancer patients whose medical record initially indicated a preference for no transfusion, 60% of guardians accepted blood products when prescribed for oncology care. Guidelines for systematic management and transfusion sparing approaches are needed to honor guardian's preferences when possible yet while maintaining equitable cancer outcomes in this population.
Treatment outcomes of standard (high dose) cisplatin and non‐standard chemotherapy for locally advanced head and neck cancer
Authors: Alamgeer Muhammad , Coleman Andrew , McDowell Lachlan , Giddings Charles , Safdar Adnan , Sigston Elizabeth , Wang Yang , Subramaniam Ashwin
Published: July 2022

Introduction

Concurrent chemoradiotherapy with high‐dose (HD) cisplatin is the standard treatment for locally advanced head and neck squamous cell carcinoma (LA‐HNSCC). Due to the higher treatment‐related adverse effects with standard therapy, alternative regimens (non‐standard therapy), namely, lower dose weekly cisplatin, carboplatin/paclitaxel, or cetuximab are considered. There is, however, no consensus on non‐standard regimens. We aimed to investigate the efficacy and safety profile of these regimens.

Methods

This single centre retrospective cohort study included all consecutive adult patients with newly diagnosed LA‐HNSCC treated with either standard or non‐standard regimens between January 2016 and April 2021. The primary outcome was 2‐year failure‐free survival (FFS). The secondary outcomes included acute toxicities, hospitalisation rates, dose modifications, treatment failure rates (TFR), and overall survival.

Results

About 235 patients were included in the final analysis; median age was 61 years (IQR 55–67), and 87% were male. Most had oropharyngeal tumours (85.5%) and p16‐positivity was frequent (80%). About 56% received non‐standard regimens: weekly cisplatin = 79 and non‐cisplatin = 48. These patients had higher Charlson Comorbidity Index (CCI; p < .001) and lower European Cooperative Oncology Group (ECOG)‐0 (p = .003). There was no difference in 2‐year FFS (hazard ratio [HR] = 1.16; 95% confidence interval – [CI] 0.65–2.05), hospitalisation and grade‐3 toxicity rates between the two regimens. Nausea and vomiting were lower in the non‐standard regimen (3.0% vs. 16%, p < .001). Dose reductions, adjusted for age, sex, and CCI, were less likely in the non‐standard regimen (OR = 2.36; 95%‐CI: 1.01–5.49, p = .007).

Conclusions

We demonstrated similar efficacy of lower dose weekly cisplatin and carboplatin/paclitaxel regimens and better safety profile of weekly cisplatin compared to standard HD cisplatin regimens for LA‐HNSCC. Multicenter randomised control trials are required in HD cisplatin‐ineligible patients.
Applications of Viologens in Organic and Inorganic Discoloration Materials
Authors: Yu Shuang , Ying Jun , Tian Aixiang
Published: July 2022

Viologen derived from 4,4’‐bipyridine has attracted much attention because of its color changing properties with electron transfer, unique redox stability and structural diversity. These characteristics have led to its successful use in various applications, in particular in color‐changing materials. In the past few years, researchers have been working on the syntheses of viologen‐based color‐changing functional materials, and such materials have been widely used in many fields. In photochromic materials, it is used as anti‐counterfeiting material; in thermochromic, it is used as memory storage material, and in electrochromic, it is used as a battery material. This Review discusses the progress of viologen in organic and inorganic discoloration materials in recent years. The syntheses of viologen and its derivatives are summarized, and its application in the field of discoloration materials is introduced.
Eating disorder behaviors as predictors of suicidal ideation among people with an eating disorder
Authors: Joiner Thomas E. , Robison Morgan , McClanahan Susan , Riddle Megan , Manwaring Jamie , Rienecke Renee D. , Le Grange Daniel , Duffy Alan , Mehler Philip S. , Blalock Dan V.
Published: July 2022

Objective

Suicidality is known to be elevated among people with an eating disorder. The aim of the current study was to examine whether any of three specific behavioral facets of eating disorders (i.e., purging, binge eating, restricting) would be the strongest predictors of suicidal ideation, controlling for one another, in longitudinal analyses from admission to discharge. We hypothesized that purging, above and beyond restricting or binge eating, would be the most important predictor of suicidal ideation.

Method

In the present study, patients with an eating disorder (N = 936), the majority of whom met criteria for a current DSM‐5 diagnosis of Anorexia Nervosa (n = 560), completed the Eating Pathology Symptoms Inventory (EPSI) and the Beck Depression Inventory II‐Item 9 suicidal ideation index, at admission and again at discharge. The settings were eating disorder treatment facilities offering inpatient, residential, partial hospitalization program (PHP), and intensive outpatient (IOP) levels of care. We pitted EPSI purging, EPSI restriction, and EPSI binge eating against one another in a regression framework predicting discharge suicidal ideation controlling for suicidal ideation at admission.

Results

EPSI Purging significantly predicted both presence/absence of suicidal ideation (β = .22, t = 2.48, p = .01; OR = 1.25, 95% CI [1.05, 1.49]) and intensity of suicidal ideation (β = .04, t = 2.31, p = .02) at discharge, whereas neither EPSI Restricting nor EPSI Binge Eating did (p > .30).

Discussion

Study results suggest that purging may have particular relevance in estimating suicide risk in patients with an eating disorder.
Forecasting shifts in habitat suitability of three marine predators suggests a rapid decline in inter‐specific overlap under future climate change
Authors: van Beest Floris M. , Dietz Rune , Galatius Anders , Kyhn Line Anker , Sveegaard Signe , Teilmann Jonas
Published: July 2022

Understanding how environmental and climate change can alter habitat overlap of marine predators has great value for the management and conservation of marine ecosystems. Here, we estimated spatiotemporal changes in habitat suitability and inter‐specific overlap among three marine predators: Baltic gray seals (Halichoerus grypus), harbor seals (Phoca vitulina), and harbor porpoises (Phocoena phocoena) under contemporary and future conditions. Location data (>200 tagged individuals) were collected in the southwestern region of the Baltic Sea; one of the fastest‐warming semi‐enclosed seas in the world. We used the maximum entropy (MaxEnt) algorithm to estimate changes in total area size and overlap of species‐specific habitat suitability between 1997–2020 and 2091–2100. Predictor variables included environmental and climate‐sensitive oceanographic conditions in the area. Sea‐level rise, sea surface temperature, and salinity data were taken from representative concentration pathways [RCPs] scenarios 6.0 and 8.5 to forecast potential climate change effects. Model output suggested that habitat suitability of Baltic gray seals will decline over space and time, driven by changes in sea surface salinity and a loss of currently available haulout sites following sea‐level rise in the future. A similar, although weaker, effect was observed for harbor seals, while suitability of habitat for harbor porpoises was predicted to increase slightly over space and time. Inter‐specific overlap in highly suitable habitats was also predicted to increase slightly under RCP scenario 6.0 when compared to contemporary conditions, but to disappear under RCP scenario 8.5. Our study suggests that marine predators in the southwestern Baltic Sea may respond differently to future climatic conditions, leading to divergent shifts in habitat suitability that are likely to decrease inter‐specific overlap over time and space. We conclude that climate change can lead to a marked redistribution of area use by marine predators in the region, which may influence local food‐web dynamics and ecosystem functioning.