bluuebunny/crossref_metadata_2025_split huggingface dataset:
The 1,3‐Dipolar Cycloaddition: From Conception to Quantum Chemical Design
Authors: Beutick Steven E. , Vermeeren Pascal , Hamlin Trevor A. 
Published: July 2022

AbstractThe 1,3‐dipolar cycloaddition (1,3‐DCA) reaction, conceptualized by Rolf Huisgen in 1960, has proven immensely useful in organic, material, and biological chemistry. The uncatalyzed, thermal transformation is generally sluggish and unselective, but the reactivity can be enhanced by means of metal catalysis or by the introduction of either predistortion or electronic tuning of the dipolarophile. These promoted reactions generally go with a much higher reactivity, selectivity, and yields, often at ambient temperatures. The rapid orthogonal reactivity and compatibility with aqueous and physiological conditions positions the 1,3‐DCA as an excellent bioorthogonal reaction. Quantum chemical calculations have been critical for providing an understanding of the physical factors that control the reactivity and selectivity of 1,3‐DCAs.In silicoderived design principles have proven invaluable for the design of new dipolarophiles with tailored reactivity. This review discusses everything from the conception of the 1,3‐DCA all the way to the state‐of‐the‐art methods and models used for the quantum chemical design of novel (bioorthogonal) reagents.
Chaos and order in a local barred galaxy model
Authors: Alrebdi Haifa I. , Zotos Euaggelos E. 
Published: July 2022

AbstractWe use an analytical gravitational model that describes the local motion of stars near the central region of a barred galaxy. By integrating and classifying large sets of starting conditions of trajectories we manage to determine how the important parameters of the bar, such as its mass, strength, scale length, and angular velocity influence the motion of stars. For the orbit taxonomy, we combine traditional dynamical methods such as the classical Poincaré surface of section along with modern chaos indicators such as the Smaller Alignment Index (SALI). Our results of the local galactic model are compared with previous studies using global gravitational models.
Influence of circadian rhythm on drug metabolism in 3D hepatic spheroids
Authors: Narayanan Vibha , Rodrigues Andre L. , Dordick Jonathan S. 
Published: July 2022

AbstractCircadian rhythms are characterized as oscillations that fluctuate based on a 24 h cycle and are responsible for regulation of physiological functions. While the internal clock synchronizes gene expression using external cues like light, a similar synchronization can be induced in vitro by incubating the cells with an increased percentage of serum followed by its rapid removal. Previous studies have suggested that synchronization of HepG2 cell line induced the rhythmic expression of drug‐metabolizing enzymes (DME) most specifically the cytochrome P450 enzymes. However, there is a lack of evidence demonstrating the influence of three‐dimensional microenvironment on the rhythmicity of these genes. To understand this interplay, gene expression of the circadian machinery and CYP450s were compared using the model human hepatocarcinoma cell line, HepG2. Upon serum shock synchronization, gene and protein expression of core clock regulators was assessed and rhythmic expression of these genes was demonstrated. Further insight into the interrelations between various gene pairs was obtained using statistical analysis. Using RNA sequencing, an in‐depth understanding of the widespread effects of circadian regulation on genes involved in metabolic processes in the liver was obtained. This study aids in the better understanding of chronopharmacokinetic events in humans using physiologically relevant 3D culture systems.
Production of a high purity, C‐tagged hepatitis B surface antigen fusion protein VLP vaccine for malaria expressed in Pichia pastoris under cGMP conditions
Authors: Mukhopadhyay Ekta , Brod Florian , Angell‐Manning Philip , Green Nicola , Tarrant Richard D. , Detmers Frank J. , Bolam Emma J. , Baleanu Ioana N. , Hobson Mark , Whale Gary , Morris Susan J. , Ashfield Rebecca , Gilbert Sarah C. , Jin Jing , Draper Simon J. , Moyle Sarah P. , Berrie Eleanor L. , Hill Adrian V. S. 
Published: July 2022

AbstractVirus‐like particles (VLPs) induce strong humoral and cellular responses and have formed the basis of some currently licensed vaccines. Here, we present the method used for the production of R21, a VLP‐based anti‐sporozoite malaria vaccine, under current Clinical Good Manufacturing Practice regulations (cGMP). Previous preclinical studies in BALB/c mice showed that R21 produced almost complete protection against sporozoite challenge with transgenic Plasmodium berghei parasites. Here, we have modified the preclinical production process to enable the production of sufficient quantities of highly pure, clinical‐grade material for use in human clinical trials. The R21 construct was re‐engineered to include a C‐tag to allow affinity‐based separation from the major contaminant alcohol oxidase 1 (AOX 1, ~74 kDa). To our knowledge, this is the first use of C‐tag technology to purify a VLP vaccine candidate for use in human clinical trials. The R21 vaccine has shown high‐level efficacy in an African Phase IIb trial, and multiple clinical trials are underway to assess the safety and efficacy of the vaccine. Our findings support the future use of C‐tag platform technologies to enable cGMP‐compliant biomanufacturing of high purity yeast‐expressed VLP‐based vaccines for early phase clinical trials when clinical grade material is required in smaller quantities in a quick time frame.
Preparation of CuCr1−xGaxO2 (0 ≤ x ≤ 1) nanocrystals for inorganic hole conductor of inverted perovskite solar cells
Authors: Choo Hyun Sue , Jo Ju Hee , Suh Woo Seok , Park You Jin , In Lee Wan 
Published: July 2022

AbstractCuGaO2 (CGO) and CuCrO2 (CCO) belonging to the delafossite family are attracting attention as potential inorganic hole‐transporting materials (HTMs) for perovskite solar cells (PSCs). Herein, various solid solutions of CCO and CGO were prepared by hydrothermal reaction to obtain an optimal composition that leads to reproducible size control and high hole conductivity. The particle sizes of the prepared CuCr1−xGaxO2 (CCGO) were maintained at ~10 nm with a high uniformity until the Ga/Cr composition ratio was increased to 60/40, whereas the samples derived at the composition ratio of 70/30 or higher contain large disk‐like structures. When they were applied as HTMs of the inverted PSC devices employing CH3NH3PbI3, the CCGO with Ga content of 60% provided the best photovoltaic properties. The achieved photovoltaic conversion efficiency was 16.38%, which is 27% and 22% higher than that of the PSCs with bare CCO and CGO, respectively.
Antibody variable region engineering for improving cancer immunotherapy
Authors: Lou Hantao , Cao Xuetao 
Published: July 2022

AbstractThe efficacy and specificity of conventional monoclonal antibody (mAb) drugs in the clinic require further improvement. Currently, the development and application of novel antibody formats for improving cancer immunotherapy have attracted much attention. Variable region‐retaining antibody fragments, such as antigen‐binding fragment (Fab), single‐chain variable fragment (scFv), bispecific antibody, and bi/trispecific cell engagers, are engineered with humanization, multivalent antibody construction, affinity optimization and antibody masking for targeting tumor cells and killer cells to improve antibody‐based therapy potency, efficacy and specificity. In this review, we summarize the application of antibody variable region engineering and discuss the future direction of antibody engineering for improving cancer therapies.
Using phenomenography to unearth factors influencing the delivery of guidance services
Authors: Sedofia John , Fia Stephen Doh , Tutu‐Danquah Cecilia 
Published: July 2022

AbstractWhich factors influence the delivery of school guidance services in Colleges of Education (CoEs) in Ghana? The guidance needs of students in the CoEs may not be fully met if the factors that influence guidance service delivery at that level of education are not explored for effective upgrade of service quality. This phenomenographic study therefore explored factors influencing the delivery of guidance services in CoEs in Ghana. We interviewed second‐year teacher trainees (n = 24) and counsellors from three randomly selected CoEs in the Volta region of Ghana (n = 3). The findings indicate that material resources and awareness influenced guidance service delivery in the CoEs. It was also found that although students reported that confidentiality and attitude influenced service delivery in the colleges, the counsellors did not agree with this. Finally, the study discovered that human resource does not influence guidance service delivery in the colleges. It was recommended that college authorities should provide the material resources, such as offices, computers, and test batteries, that are needed for counselling, and counsellors should publicise the guidance programme to raise awareness and lead to the development of positive attitudes towards the programme. This study contributes to the guidance and counselling literature by illuminating the factors influencing guidance service delivery in CoEs. This should be of interest to practitioners, policymakers and researchers in school guidance and counselling.
Opportunities and Challenges to Profile mRNA Modifications in Escherichia coli**
Authors: Petrov Dimitar Plamenov , Kaiser Steffen , Kaiser Stefanie , Jung Kirsten 
Published: July 2022

AbstractmRNA methylation is an important regulator of many physiological processes in eukaryotes but has not been studied in depth in prokaryotes. Working with bacterial mRNA is challenging because it lacks a poly(A)‐tail. However, methods for detecting RNA modifications, both sequencing and mass spectrometry, rely on efficient preparation of mRNA. Here, we compared size‐dependent separation by electrophoresis and rRNA depletion for enrichment of Escherichia coli mRNA. The purification success was monitored by qRT‐PCR and RNA sequencing. Neither method allowed complete removal of rRNA. Nevertheless, we were able to quantitatively analyze several modified nucleosides in the different RNA types. We found evidence for stress dependent RNA modification reprofiling in rRNA, but also several modified nucleosides in the mRNA enriched fractions showed significant changes.
The role of metal ions in the Golgi apparatus
Authors: Gao Jiayin , Gao Anbo , Zhou Hong , Chen Linxi 
Published: July 2022

AbstractThe Golgi apparatus is a membrane‐bound organelle that functions as a central role in the secretory pathway. Since the discovery of the Golgi apparatus, its structure and function have attracted ever‐increasing attention from researchers. Recently, it has been demonstrated that metal ions are necessary for the Golgi apparatus to maintain its proper structure and functions. Given that metal ions play an important role in various biological processes, their abnormal homeostasis is related to many diseases. Therefore, in this paper, we reviewed the uptake and release mechanisms of the Golgi apparatus Ca2+, Cu, and Zn2+. Furthermore, we describe the diseases associated with Golgi apparatus Ca2+, Cu, and Zn2+ imbalance.
PRospective REgistry of PAtients in REfractory cardiogenic shock—The PREPARE CardShock registry
Authors: von Lewinski Dirk , Herold Lukas , Stoffel Christian , Pätzold Sascha , Fruhwald Friedrich , Altmanninger‐Sock Siegfried , Kolesnik Ewald , Wallner Markus , Rainer Peter , Bugger Heiko , Verheyen Nicolas , Rohrer Ursula , Manninger‐Wünscher Martin , Scherr Daniel , Renz Dietmar , Yates Ameli , Zirlik Andreas , Toth Gabor G. 
Published: July 2022

AbstractAimCardiogenic shock (CS) is a hemodynamically complex multisystem syndrome associated with persistently high morbidity and mortality. As CS is characterized by progressive failure to provide adequate systemic perfusion, supporting end‐organ perfusion using mechanical circulatory support (MCS) seems intriguing. Since most patients with CS present in the catheterization laboratory, percutaneously implantable systems have the widest adoption in the field. We evaluated feasibility, outcomes, and complications after the introduction of a full‐percutaneous program for both the Impella CP device and venoarterial extracorporeal membrane oxygenator (VA‐ECMO).MethodsPREPARE CardShock (PRospective REgistry of PAtients in REfractory cardiogenic shock) is a prospective single‐center registry, including 248 consecutive patients between May 2019 and April 2021, who underwent cardiac catheterization and displayed advanced cardiogenic shock. The median age was 70 (58–77) years and 28% were female. Sixty‐five percent of the cases had cardiac arrest, of which 66% were out‐of‐hospital cardiac arrest. A local standard operating procedure (SOP) indicating indications as well as relative and absolute contraindications for different means of MCS (Impella CP or VA‐ECMO) was used to guide MCS use. The primary endpoint was in‐hospital death and secondary endpoints were spontaneous myocardial infarction and major bleedings during the hospital stay.ResultsOverall mortality was 50.4% with a median survival of 2 (0–6) days. Significant independent predictors of mortality were cardiac arrest during the index event (odds ratio [OR] with 95% confidence interval [CI]: 2.53 [1.43–4.51]; p = 0.001), age > 65 years (OR: 2.05 [1.03–4.09]; p = 0.036]), pH < 7.30 (OR: 2.69 [1.56–4.66]; p < 0.001), and lactate levels > 2 mmol/L (OR: 4.51 [2.37–8.65]; p < 0.001).ConclusionsConclusive SOPs assist target‐orientated MCS use in CS. This study provides guidance on the implementation, validation, and modification of newly established MCS programs to aid centers that are establishing such programs.
Particle Size Effects in the Selective Hydrogenation of Alkadienes over Supported Cu Nanoparticles
Authors: Totarella Giorgio , de Rijk Jan Willem , Delannoy Laurent , de Jongh Petra E. 
Published: July 2022

AbstractCopper is considered an excellent alternative to noble‐metal selective hydrogenation catalysts. Herein, we systematically studied the effect of Cu nanoparticle size (2–10 nm) in the selective hydrogenation of 1,3‐butadiene in excess of propene. The catalysts exhibited particle size‐dependent activity, with particles above 4 nm being 3 to 4 times more active than the 2 nm ones, and at the same time more selective (up to 99 % at almost full butadiene conversion for 7–10 nm particles). The higher activity of larger particles was ascribed to a higher fraction of kinks and step sites, essential to activate hydrogen. The high selectivity of nanoparticulate Cu catalysts was explained by a very strong preferential adsorption of 1,3‐butadiene compared to mono‐olefin adsorption on the Cu surface (in particular on larger particles), as proven via adsorption measurements. These findings may guide both testing and catalyst design for reactions where hydrogen surface availability and selectivity play a key role.
Selective Hydrogenation of L‐proline to L‐prolinol over Al2O3‐supported Pt‐MoOx Catalyst
Authors: Kaku Chinami , Suganuma Satoshi , Nakajima Kiyotaka , Tsuji Etsushi , Katada Naonobu 
Published: July 2022

AbstractL‐proline, one of abundant amino acids, can be utilized as a biobased feedstock for the synthesis of an amino alcohol, L‐prolinol, which serves as chiral auxiliary in a variety of asymmetric synthesis. Herein we examined selective hydrogenation of L‐proline into L‐prolinol over M−MoOx/Al2O3 (M=Pt, Rh, Pd, and Ru) in aqueous H3PO4 solution. Pt‐MoOx/Al2O3 exhibited high activity among the catalysts, affording L‐prolinol in 75 % selectivity and >99.9 % enantiomeric excess, while Pt/Al2O3 was inactive. Mo species were highly dispersed as a polyoxo cluster on both Pt nanoparticles and Al2O3 support, and participated concertedly with Pt nanoparticles in the hydrogenation. Activated carboxyl group of L‐proline by MoOx species on Pt nanoparticle are readily hydrogenated with dissociative hydrogen formed on the same Pt nanoparticle with MoOx species, giving an effective route for the hydrogenation of L‐proline. Pt‐MoOx/Al2O3 could be identified as an active and reusable catalyst due to no loss of its original activity.
Exogenous Ligand‐Free Nickel‐Catalyzed Carboxylate O‐Arylation: Insight into NiI/NiIII Cycles**
Authors: Wolzak Lukas A. , de Zwart Felix J. , Oudsen Jean‐Pierre H. , Bartlett Stuart A. , de Bruin Bas , Reek Joost N. H. , Tromp Moniek , Korstanje Ties J. 
Published: July 2022

AbstractNickel‐catalyzed cross‐coupling reactions have become a powerful methodology to construct C‐heteroatom bonds. However, many protocols suffer from competitive off‐cycle reaction pathways and require non‐equimolar amounts of coupling partners to suppress them. Here, we report on mechanistic examination of carboxylate O‐arylation under thermal conditions, in both the presence and absence of an exogeneous bipyridine‐ligand. Furthermore, spectroscopic studies of the novel ligand‐free carboxylate O‐arylation reaction unveiled the resting state of the nickel catalyst, the crucial role of the alkylamine base and the formation of an off‐cycle NiI−NiII dimer upon reduction. This study provides insights into the competition between productive catalysis and deleterious pathways (comproportionation and protodehalogenation) in the commonly proposed self‐sustained NiI/NiIII catalytic cycle. Thereby we show that for productive nickel‐catalyzed carboxylate O‐arylation a choice must be made between either mild conditions or equimolar ratios of substrates.
Reaction Kinetics of an Industrial Front‐End Acetylene Hydrogenation Catalyst Using the Advanced TEMKIN Reactor
Authors: Hock Sebastian , Iser Leonhard , Lucas Martin , Rose Marcus 
Published: July 2022

AbstractThe front‐end process integration of the selective acetylene hydrogenation provides several advantages over the tail‐end option. But extensive knowledge of the process and reaction kinetics are required. This work combines the ideal conditions of the advanced TEMKIN reactor in a laboratory plant for gradient‐free kinetic analysis of eggshell catalyst under industrially relevant front‐end conditions. With this system an industrial state of the art Pd‐Ag/Al2O3 eggshell catalyst is investigated and the temperature dependent data under various feed compositions including information on the formation of C4‐species are reported.
Effect of Nanoscale Confinement on Ultrafast Dynamics of Singlet Fission in TIPS‐Pentacene
Authors: Silori Yogita , Chawla Sakshi , Yadav Anita , De Arijit K. 
Published: July 2022

AbstractSinglet fission (SF) is a phenomenon for the generation of a pair of triplet excitons from anexcited molecule in singlet electronic state interacting with another adjacent molecule in its ground electronic state. By increasing the effective number of charge carriers and reducing thermal dissipation of excess energy, SF is promised to enhance light‐harvesting efficiency for photovoltaic applications. While SF has been extensively studied in thin films and crystals, the same has not been explored much within a confined medium. Here, we report the ultrafast SF dynamics of triisopropylsilylethynyl pentacene (TIPS‐Pn) in micellar nanocavity of varying sizes (prepared from TX‐100, CTAB, and SDS surfactants). The nanoparticles with a smaller size contain weakly coupled chromophores which are shown to be more efficient for SF followed by triplet generation as compared to the nanoparticles of larger size which contain strongly coupled chromophores which are less efficient due to the presence of singlet exciton traps. Through these studies, we delineate how a subtle interplay between short‐range and long‐range interaction among chromophores confined within nanoparticles, fine‐tuned by the curvature of the micellar interface but irrespective of the nature of the micelle (cationic or anionic or neutral), play a crucial role in SF through and generation of triplets.
DNA Tetrahedron Framework Guided Conjugation and Assembly of Gold Nanoparticles
Authors: He Wei , Zhao Yan , Xing Shu , Zhang Yinan , Wang Lihua , Liu Huajie 
Published: July 2022

AbstractAu nanoparticles (AuNPs) have been extensively used to assemble programmable structures that feature various functions. One central challenge of precisely directed assembly is to make valence‐programmable building blocks. Herein, we use the DNA tetrahedron framework to stoichiometrically conjugate to Au nanoparticles, which results in monovalent building blocks at nanometer scale. We further fabricated high‐order Au‐tetrahedron structures to verify the ability of the blocks for building assemblies. These structures represent an exploration of an avenue to monovalent AuNPs, and provide the feasibility of precisely manipulating nanoparticles into prescribed assemblies.
Cross Dehydrogenative Coupling of Chloro‐ and Fluoroalkanes with Methylarenes
Authors: Xiang Jia‐Xiang , Patureau Frederic W. 
Published: July 2022

AbstractCross dehydrogenative coupling reactions (CDCs) are considerably more step‐ and atom efficient compared to classical cross coupling methods. In this context, the photochemical CDCs of hydrochlorocarbons and hydrofluorocarbons with methylarenes are herein described. This unprecedented CDC reaction concept enables a new retrosynthetic cut for the selective construction of valuable chlorinated and fluorinated organic skeletons, from industrially important dichloromethane, dichloroethane, difluoromethane (HFC‐32), and 1,1,1,2‐tetrafluoroethane (HFC‐134a).
Methods to Identify Immune Cells in Tissues With a Focus on Skin as a Model
Authors: Murphy Peter R. , Narayanan Divyaa , Kumari Snehlata 
Published: July 2022

AbstractThe skin protects our body from external challenges, insults, and pathogens and consists of two layers, epidermis and dermis. The immune cells of the skin are an integral part of protecting the body and essential for mediating skin immune homeostasis. They are distributed in the epidermal and dermal layers of the skin. Under homeostatic conditions, the mouse and human skin epidermis harbors immune cells such as Langerhans cells and CD8+ T cells, whereas the dermis contains dendritic cells (DCs), mast cells, macrophages, T cells, and neutrophils. Skin immune homeostasis is maintained through communication between epidermal and dermal cells and soluble factors. This communication is important for proper recruitment of immune cells in the skin to mount immune responses during infection/injury or in response to external/internal insults that alter the local cellular milieu. Imbalance in this crosstalk that occurs in association with inflammatory skin disorders such as psoriasis and atopic dermatitis can lead to alterations in the number and type of immune cells contributing to pathological manifestation in these disorders. Profiling changes in the immune cell type, localization, and number can provide important information about disease mechanisms and help design interventional therapeutic strategies. Toward this end, skin cells can be detected and characterized using basic techniques like immunofluorescence, immunohistochemistry, and flow cytometry, and recently developed methods of multiplexing. This article provides an overview on the basic techniques that are widely accessible to researchers to characterize immune cells of the skin. © 2022 The Authors. Current Protocols published by Wiley Periodicals LLC.