bluuebunny/crossref_metadata_2025 huggingface dataset:
Procesy evropské defragmentace jako inspirativní nástroj policymaking
Authors: Váňa Tomáš
Published: November 2013

This paper looks at the different stages of European municipal defragmentation and at the diverse models that post-war countries have adopted for their municipal structures. It notes that defragmentation has been undertaken with little previous knowledge regarding the possible impacts of these approaches. Through applying the QCA method of analysis it looks at common and distinct features of these approaches and draws a sharp dichotomy between defragmentation trends in post-communist countries and countries of the Western bloc. By showing that there are trends intrinsic to post-communist political systems, this paper presents the idea that these systems can learn from errors made by countries that approached municipal defragmentation before them. Drawing on the example of the late-defragmenting Iceland, this paper shows how currently or prospectively defragmenting countries can learn from its experience. In the last part of the paper, suggestions are made with regard to how the Czech Republic can learn from this experience, particularly from democratic referendums, legislative and economic incentives, and municipal cooperation.
Konceptualizácia a meranie variácií kapitalizmu v nových členských štátoch EÚ: Kritické zhodnotenie
Authors: Baboš Pavol
Published: November 2013

Almost a decade has passed since the first post-communist states acceded to the EU. Ten years after confirmation of the successful establishment of democratic and market-economic institutions in these countries, it is time to ask what type of institutions really developed. This article critically reviews contemporary research into capitalism in the eight countries, the main approaches applied, and the findings published. Firstly, it attempts to identify the type of capitalism that has developed in the region. Secondly, it highlights some pitfalls in the contemporary study of capitalism in Central Eastern Europe and discusses possible remedies for future research. The main recommendation, discussed in more detail in the study, is that stricter theoretical reasoning would help to eliminate the contradictory conclusions many authors have arrived at.
Opoziční smlouvy „za kopečky“ I.: Byl pakt ČSSD a ODS z let 1998–2002 demokratickou deviací?
Authors: Kopeček Lubomír
Published: November 2013

After the 1998 general elections to the Chamber of Deputies of the Czech Republic, the largest party, the Social Democratic Party (ČSSD), formed a minority government. The origin and existence of this government was enabled by an agreement with the second largest formation, the Civic Democratic Party (ODS). What was then known as the Opposition Agreement became the subject of considerable debate. The paper analyses the Opposition Agreement in comparison with other minority governments with external support, be they governments formed on the basis of ad hoc agreements or complex ones. The text looks in detail at government practice in Denmark, Sweden, New Zealand, and Italy at the time of the Historic Compromise; this is then used as a context for outlining the specifics of the Czech case. The paper highlights not only the Opposition Agreement between the Social Democrats and the Civic Democratic Party and the later Toleration Patent, which even deepened the cooperation between these two parties, but also the frequent ad hoc legislative coalitions which the minority government was able to form. An additional aim of the paper is to outline foreign analogies to the potential future single-party minority government of the Czech Social Democrats supported by the Communists. Because of its considerable length, the text is divided into two parts; the first part is printed in this volume.
Phylogeny of Miliusa (Magnoliales: Annonaceae: Malmeoideae: Miliuseae), with descriptions of two new species from Malesia – Corrigendum
Authors: Chaowasku Tanawat , Keßler Paul J.A. , Chatrou Lars
Published: November 2013

no abstract
Diversidade e educação especial em diálogos: reflexões sobre os discursos da inclusão
Authors: Osório Antônio Carlos Do Nascimento , Leão Tatiana Calheiros Lapas
Published: November 2013

http://dx.doi.org/10.5902/1984686X8269Este artigo trata de questões referentes à produção dos discursos sobre a inclusão, tendo como ponto de apoio aqueles direcionados aos alunos da educação especial no processo de escolarização nas escolas ditas comuns. O aporte teórico e metodológico tem como base os referenciais de Michel Foucault e suas possibilidades epistemológicas de compreensões, enquanto uma problematização cercada por um imaginário social sobre as possibilidades de uma inclusão. Para Foucault (1975), a valorização da diversidade se imbrica na formação do conceito de anormalidade, com os princípios de verdade e justiça, no grotesco exercício da mecânica do poder, saber em vista a um sujeito dito diferente. Estabeleceu-se como objetivo, nesta discussão, uma reflexão de alguns arquivos que antecederam as orientações dos subsídios do documento elaborado como Política Nacional de Educação Especial. Nessa reflexão, sob a perspectiva da inclusão, são demonstrados suas possibilidades e seus limites de transgressão, deixando evidente que isto não se limita aos aspectos relacionados às práticas pedagógicas e, sim, às práticas sociais demarcadas por um arsenal de preconceitos. Os resultados revelaram que, no momento atual, os discursos produzidos sobre a inclusão escolar, contidos nesses arquivos, trazem o exame como estratégia de aglutinação, permitindo um melhor controle das diferenças e que as instituições escolares, embora não venham dando conta nem daqueles alunos ditos normais, são responsáveis por essa correção social. Tais condições geram uma variedade de diferentes desafios à estrutura escolar, fruto de distorções acumuladas pelo desvio de seus propósitos, como sendo campo de conflitos e espaço para reforço das diferenças sociais.
The Effects of Topical Agent (Kelo-Cote or Contractubex) Massage on the Thickness of Post-Burn Scar Tissue Formed in Rats
Authors: Ko Won Jin , Na Young Cheon , Suh Bum Sin , Kim Hyeon A , Heo Woo Hoe , Choi Gum Ha , Lee Seo Ul
Published: November 2013

Background We conducted an experimental study to compare the effect of massage using topical agents (Kelo-cote or Contractubex) on scar formation by massaging the healed burn wound on the dorsal area of Sprague-Dawley (SD) rats.

Methods Four areas of second degree contact burn were made on the dorsal area of each of 15 SD rats, using a soldering iron 15 mm in diameter. After gross epithelialization in the defect, 15 SD rats were randomly divided into four groups: the Kelo-cote group, Contractubex group, Vaseline group, and control group. Rats in three of the groups (all but the Control group) were massaged twice per day for 5 minutes each day, while those in the Control group were left unattended. For histologic analysis, we performed a biopsy and evaluated the thickness of scar tissue.

Results In the Kelo-cote and Contractubex groups, scar tissue thicknesses showed a significant decrease, compared with the Vaseline and control groups. However, no significant differences were observed between the Kelo-cote and Contractubex groups. In the Vaseline group, scar tissue thicknesses showed a significant decrease, compared with the control groups.

Conclusions The findings of this study suggest that massage using a topical agent is helpful in the prevention of scar formation and that massage only with lubricant (no use of a topical agent) also has a considerable effect, although not as much as the use of a topical agent. Thus, we recommend massage with a topical agent on the post-burn scar as an effective method for decreasing the scar thickness.
Reconstruction of Various Perinasal Defects Using Facial Artery Perforator-Based Nasolabial Island Flaps
Authors: Yoon Tae Ho , Yun In Sik , Rha Dong Kyun , Lee Won Jai
Published: November 2013

Background Classical flaps for perinasal defect reconstruction, such as forehead or nasolabial flaps, have some disadvantages involving limitations of the arc of rotation and two stages of surgery. However, a perforator-based flap is more versatile and allows freedom in flap design. We introduced our experience with reconstruction using a facial artery perforator-based propeller flap on the perinasal area. We describe the surgical differences between different defect subtypes.

Methods Between December 2005 and August 2013, 10 patients underwent perinasal reconstruction in which a facial artery perforator-based flap was used. We divided the perinasal defects into types A and B, according to location. The operative results, including flap size, arc of rotation, complications, and characteristics of the perforator were evaluated by retrospective chart review and photographic evaluation.

Results Eight patients were male and 2 patients were female. Their mean age was 61 years (range, 35-75 years). The size of the flap ranged from 1 cm×1.5 cm to 3 cm×6 cm. Eight patients healed uneventfully, but 2 patients presented with mild flap congestion. However, these 2 patients healed by conservative management without any additional surgery. All of the flaps survived completely with aesthetically pleasing results.

Conclusions The facial artery perforator-based flap allowed for versatile customized flaps, and the donor site scar was concealed using the natural nasolabial fold.
A Clinical Anatomic Study of Internal Mammary Perforators as Recipient Vessels for Breast Reconstruction
Authors: Baek In-Soo , You Jae-Pil , Rhee Sung-Mi , Son Gil-Su , Kim Deok-Woo , Dhong Eun-Sang , Park Seung-Ha , Yoon Eul-Sik
Published: November 2013

Background Partially resecting ribs of the recipient site to facilitate easy anastomosis of the internal mammary vessels to free flaps during breast reconstruction can cause chest wall pain or deformities. To avoid this, the intercostal perforating branches of the internal mammary vessels can be used for anastomosis. The purpose of this study was to investigate the location and size of the internal mammary perforator vessels based on clinical intraoperative findings and to determine their reliability as recipient vessels for breast reconstruction with microsurgical free tissue transfer.

Methods Twelve patients were preoperatively screened for the presence of internal mammary perforators using Doppler tracing. After modified radical mastectomy was performed by a general surgeon, the location and size of the internal mammary perforator vessels were microscopically investigated. The external diameter was examined using a vessel-measuring gauge from a mechanical coupling device, and the distance from the mid-sternal line to the perforator was also measured.

Results The largest arterial perforator averaged 1.5 mm, and the largest venous perforator averaged 2.2 mm. Perforators emerging from the second intercostal space had the largest average external diameter; the second intercostal space also had the largest number of perforators arising from it. The average distance from the mid-sternal line to the perforator was 20.2 mm.

Conclusions Internal mammary perforators presented consistent and reliable anatomy in this study. Based on these results, the internal mammary perforators appear to have a suitable diameter for microvascular anastomosis and should be considered as an alternative recipient vessel to the internal mammary vessel.
Comparative Study of Spiral Oblique Retinacular Ligament Reconstruction Techniques Using Either a Lateral Band or a Tendon Graft
Authors: Oh Jae Yun , Kim Jin Soo , Lee Dong Chul , Yang Jae Won , Ki Sae Hwi , Jeon Byung Joon , Roh Si Young
Published: November 2013

Background In the management of mallet deformities, oblique retinacular ligament (ORL) reconstruction provides a mechanism for automatic distal interphalangeal (DIP) joint extension upon active proximal interphalangeal joint extension. The two variants of ORL reconstruction utilize either the lateral band or a free tendon graft. This study aims to compare these two surgical techniques and to assess any differences in functional outcome. As a secondary measure, the Mitek bone anchor and pull-in suture methods are compared.

Methods A single-institutional retrospective review of ORL reconstruction was performed. The standard patient demographics, injury mechanism, type of ORL reconstruction, and pre/postoperative degree of extension lag were collected for the 27 cases identified. The cases were divided into lateral band (group A, n=15) and free tendon graft groups (group B, n=12). Group B was subdivided into the pull-in suture technique (B-I) and the Mitek bone anchor method (B-II).

Results Overall, ORL reconstructions had improved the mean DIP extension lag by 10° (P=0.027). Neither the reconstructive technique choice nor bone fixation method identified any statistically meaningful difference in functional outcome (P=0.51 and P=0.83, respectively). Soft-tissue injury was associated with 30.8° of improvement in the extension lag. The most common complications were tendon adhesion and rupture.

Conclusions The choice of the ORL reconstructive technique or the bone anchor method did not influence the primary functional outcome of extension lag in this study. Both lateral band and free tendon graft ORL reconstructions are valid treatment methods in the management of chronic mallet deformity.
Fragment‐based discovery of small molecule inhibitors of the HDGFRP2 PWWP domain
Authors: Wei Xiaoli , Li Shuju , Li Zihuan , Wang Lei , Fan Weiwei , Ruan Ke , Gao Jia
Published: July 2024

The PWWP domain of hepatoma‐derived growth factor‐related protein 2 (HDGFRP2) recognizes methylated histones to initiate the recruitment of homologous recombination repair proteins to damaged silent genes. The combined depletion of HDGFRP2 and its paralog PSIP1 effectively impedes the onset and progression of diffuse intrinsic pontine glioma (DIPG). Here, we discovered varenicline and 4‐(4‐bromo‐1H‐pyrazol‐3‐yl) pyridine (BPP) as inhibitors of the HDGFRP2 PWWP domain through a fragment‐based screening method. The complex crystal structures reveal that both Varenicline and BPP engage with the aromatic cage of the HDGFRP2 PWWP domain, albeit via unique binding mechanisms. Notably, BPP represents the first single‐digit micromolar inhibitor of the HDGFRP2 PWWP domain with a high ligand efficiency. As a dual inhibitor targeting both HDGFRP2 and PSIP1 PWWP domains, BPP offers an exceptional foundation for further optimization into a chemical tool to dissect the synergetic function of HDGFRP2 and PSIP1 in DIPG pathogenesis.
Impacts of polycultural cropping on crop yields and biodiversity: A systematic map protocol
Authors: Martinez Daisy A. , Gathorne‐Hardy Alfred , Smith Barbara M.
Published: July 2024

Agriculture is currently the largest driver of biodiversity‐loss worldwide. There is a critical need to develop agricultural systems that protect and promote biodiversity, while also meeting local and global food needs. Ecological theory suggests that cultivating crops in diverse mixtures both maximises niche occupancy and generates additional niches, generating both higher yields and higher biodiversity than cultivation in monocultures. A large and growing body of agronomic research provides strong evidence for the potential productivity and biodiversity benefits of in‐field crop‐diversification strategies. This protocol sets out a methodology for a systematic map of evidence on yield‐ and biodiversity‐outcomes in ‘polycultures’—systems of cultivation where multiple food crop species are grown together simultaneously at field‐scale.

Systematic searches with a global scope will be conducted in Web of Science Core Collection, Scopus, and CAB Abstracts to yield a comprehensive sample of relevant published, peer‐reviewed literature. The articles returned by searches will be subject to eligibility screening according to pre‐defined inclusion criteria, at successive stages (title and abstract, and full text). Following this, we will extract data from eligible studies on study designs, survey and sampling protocols, experimental treatments and comparators, and outcomes measured.

A narrative synthesis, illustrated by tables, figures and maps, will describe the quantity and characteristics of the available evidence on the impacts of polycultural cropping on (i) crop yields, and (ii) agroecosystem biodiversity. We will also identify the research that examines these two outcomes in parallel. The synthesis will be accompanied by a published database containing bibliographic information as well as data (see ‘2’) on study characteristics and outcomes.

Practical implications. The anticipated systematic map will provide a synthesis of current evidence regarding the potential yield‐ and biodiversity‐impacts of polycultural cropping. We will identify key knowledge gaps, and ‘clusters’ of related evidence that could lend themselves to further quantitative synthesis via subsequent systematic reviews and/or meta‐analyses. As such, the work will facilitate future appraisal of the potential of polyculture as a tool to bridge the currently conflicting priorities of food production on the one hand and biodiversity conservation on the other.
Implementation of the EU AI act calls for interdisciplinary governance
Authors: Zhong Huixin
Published: July 2024

The European Union Parliament passed the EU AI Act in 2024, which is an important milestone towards the world's first comprehensive AI law to formally take effect. Although this is a significant achievement, the real work begins with putting these rules into action, a journey filled with challenges and opportunities. This perspective article reviews recent interdisciplinary research aimed at facilitating the implementation of the prohibited AI practices outlined in the EU AI Act. It also explores the necessary future efforts to effectively enforce the banning of those prohibited practices across the EU market and the challenges associated with such enforcement. Addressing these future tasks and challenges calls for the establishment of an interdisciplinary governance framework. This framework may contain a workflow that can identify the necessary expertise and coordinate experts’ collaboration at different stages of AI governance. Additionally, it involves developing and implementing a set of compliance and ethical safeguards to ensure effective management and supervision of AI practices.
Evaluation of knowledge‐based planning models for male pelvic CBCT‐based online adaptive radiotherapy on conventional linear accelerators
Authors: Tegtmeier Riley C. , Clouser Edward L. , Laughlin Brady S. , Santos Toesca Diego A. , Flakus Mattison J. , Bashir Sara , Kutyreff Christopher J. , Hobbis Dean , Harrington Daniel P. , Smetanick Jennifer L. , Yu Nathan Y. , Vargas Carlos E. , James Sarah E. , Rwigema Jean‐Claude M. , Rong Yi
Published: July 2024

Purpose

To assess the practicality of employing a commercial knowledge‐based planning tool (RapidPlan) to generate adapted intact prostate and prostate bed volumetric modulated arc therapy (VMAT) plans on iterative cone‐beam computed tomography (iCBCT) datasets.

Methods and materials

Intact prostate and prostate bed RapidPlan models were trained utilizing planning data from 50 and 44 clinical cases, respectively. To ensure that refined models were capable of producing adequate clinical plans with a single optimization, models were tested with 50 clinical planning CT datasets by comparing dose‐volume histogram (DVH) and plan quality metric (PQM) values between clinical and RapidPlan‐generated plans. The RapidPlan tool was then used to retrospectively generate adapted VMAT plans on daily iCBCT images for 20 intact prostate and 15 prostate bed cases. As before, DVH and PQM metrics were utilized to dosimetrically compare scheduled (iCBCT Verify) and adapted (iCBCT RapidPlan) plans. Timing data was collected to further evaluate the feasibility of integrating this approach within an online adaptive radiotherapy workflow.

Results

Model testing results confirmed the models were capable of producing VMAT plans within a single optimization that were overall improved upon or dosimetrically comparable to original clinical plans. Direct application of RapidPlan on iCBCT datasets produced satisfactory intact prostate and prostate bed plans with generally improved target volume coverage/conformality and rectal sparing relative to iCBCT Verify plans as indicated by DVH values, though bladder metrics were marginally increased on average. Average PQM values for iCBCT RapidPlans were significantly improved compared to iCBCT Verify plans. The average time required [in mm:ss] to generate adapted plans was 06:09 ± 02:06 (intact) and 07:12 ± 01:04 (bed).

Conclusion

This study demonstrated the feasibility of leveraging RapidPlan to expeditiously generate adapted VMAT intact prostate and prostate bed plans on iCBCT datasets. In general, adapted plans were dosimetrically improved relative to scheduled plans, emphasizing the practicality of the proposed approach.
Neutrophil‐to‐lymphocyte ratio and longitudinal cognitive performance in Parkinson's disease
Authors: Lucero Jenniffer , Gurnani Ashita , Weinberg Janice , Shih Ludy C
Published: July 2024

Objective

Previous studies have suggested a link between peripheral inflammation and cognitive outcomes in the general population and individuals with Parkinson's disease (PD). We sought to test the association between peripheral inflammation, measured by the neutrophil‐to‐lymphocyte ratio (NLR), cognitive performance, and mild cognitive impairment (MCI) status in individuals with PD.

Methods

A retrospective, longitudinal analysis was carried out using data from the Parkinson's Progression Markers Initiative (PPMI), including 422 participants with PD followed over 5 years. Cognitive performance was assessed using a neuropsychological battery including the Montreal Cognitive Assessment (MoCA) and tests of verbal learning, visuospatial function, processing speed, and executive function. Mixed‐effect regression models were used to analyze the association between NLR, cognitive performance, and MCI status, controlling for age, sex, education, APOE genotype, and motor severity.

Results

There was a negative association between NLR and MoCA, even after adjusting for covariates (b = −0.12, p = 0.033). MoCA scores for individuals in the high NLR category exhibited a more rapid decline over time compared to the low NLR group (b = −0.16, p = 0.012). Increased NLR was associated with decreased performance across all cognitive domains. However, NLR was not associated with MCI status over 5 years of follow‐up.

Interpretation

This study demonstrates a link between elevated NLR and cognitive performance in PD, but not with MCI status over 5 years. This suggests that NLR is more strongly associated with day‐to‐day cognitive performance than with incident MCI, but this requires further study in more heterogeneous cohorts.
Nationally prominent treatment group shuts facilities amid financial ruin
Authors: Enos Gary
Published: July 2024

A three‐state addiction treatment operation that had earned accolades from quality‐of‐care evaluators and patients alike was left in tatters in recent weeks, plagued by draining finances and shattered by the suicides of two of its top administrators.
What about nicotine?
Authors: de Miranda John
Published: July 2024

“People smoke for the nicotine but die from the tar.” Michael Russell, a psychiatrist who was an early proponent of nicotine's role in cigarette addiction and developed smoking‐cessation therapies. Born on March 9, 1932, in Cape Town, South Africa, he died of a heart attack on July 16, 2009, in Cape Town.
Microfluidics as a Powerful Tool to Investigate Microvascular Dysfunction in Trauma Conditions: A Review of the State‐of‐the‐Art
Authors: Bathrinarayanan P. Vasanthi , Hallam S. M. , Grover L. M. , Vigolo D. , Simmons M. J. H.
Published: July 2024

Skeletal muscle trauma such as fracture or crush injury can result in a life‐threatening condition called acute compartment syndrome (ACS), which involves elevated compartmental pressure within a closed osteo‐fascial compartment, leading to collapse of the microvasculature and resulting in necrosis of the tissue due to ischemia. Diagnosis of ACS is complex and controversial due to the lack of standardized objective methods, which results in high rates of misdiagnosis/late diagnosis, leading to permanent neuro‐muscular damage. ACS pathophysiology is poorly understood at a cellular level due to the lack of physiologically relevant models. In this context, microfluidics organ‐on‐chip systems (OOCs) provide an exciting opportunity to investigate the cellular mechanisms of microvascular dysfunction that leads to ACS. In this article, the state‐of‐the‐art OOCs designs and strategies used to investigate microvasculature dysfunction mechanisms is reviewed. The differential effects of hemodynamic shear stress on endothelial cell characteristics such as morphology, permeability, and inflammation, all of which are altered during microvascular dysfunction is highlighted. The article then critically reviews the importance of microfluidics to investigate closely related microvascular pathologies that cause ACS. The article concludes by discussing potential biomarkers of ACS with a special emphasis on glycocalyx and providing a future perspective.
Multifunctional Recyclable Glassy Polymeric Materials
Authors: Zhang Zhenqiang , Xie Qingyi , Zhang Guoliang , Ma Chunfeng , Zhang Guangzhao
Published: July 2024

Multifunctional recyclable glassy polymeric materials (GPMs) are sustainable substitutes for high‐performance protective materials in aerospace, transportation, construction, and electronics; however, only a few such materials have been reported. This study presents a novel material design including the modular construction, utilization of self‐reinforcing polysilsesquioxane (POSS), and self‐enrichment strategy to integrate multifunctions in recyclable GPMs. Specifically, rigid self‐reinforcing thiol‐capped POSS (module 1) are connected with isocyanate‐terminated polyurethane precursors (module 2) by forming dynamic thiourethane covalent bonds to fabricate recyclable GPMs. Particularly, based on the modular construction and self‐enrichment strategy, functional module 3 can be introduced to endow recyclable GPMs with programmable multifunctionality. Demonstrating remarkable properties, including high transparency (>85% transmittance), hardness (up to 5H), good flexibility, and exceptional wear resistance, these materials also exhibit impressive shape reconfigurability and robustness after numerous thermal recycling or remolding cycles. Moreover, the introduction of functional module 3 (e.g., polydimethylsiloxane prepolymer) can self‐enrich onto the surface to endow the materials with anti‐liquid adhesion, self‐cleaning, and deicing properties while having a slight impact on their mechanical properties. This study presents a universal and tunable approach for the future design of multifunctional recyclable GPMs applicable in flexible electronics, aircraft vehicles, and architectural windows.
Commercial Carbon Fibers as Host for Sodium Deposition to Achieve High Volumetric Capacity
Authors: Ji Tianyi , Liu Xiaoxu , Wang Tian , Shi Yunli , Sheng Dawei , Hao Xiaodong , He Chaozheng , Shen Zexiang
Published: July 2024

The advancement of flexible electronic devices necessitates the utilization of electrode materials that offer robustness and high capacity. In this paper, it is revealed that commercially available carbon fibers with specific microcrystalline structures not only have high mechanical strength but also a high volumetric capacity of up to 300 mAh cm−3, surpassing conventional carbon materials. When multiple structural parameters of carbon fiber reach certain thresholds, a breakthrough in sodium storage capacity and rate performance can be achieved. This study further elucidates the mechanism whereby this specific carbon fiber primarily utilizes an all‐plateau sodium deposition mechanism, which occurs in pore‐like grain boundaries. Through in situ spectroscopy and synchrotron techniques, the reversible deposition process of metallic sodium has been revealed at different scales. Theoretical calculations and thermodynamic principles further confirm the desolvation and deposition mechanisms in carbon fibers. As a result, this research discovers the modulating effects and patterns of crystallinity, defect, and orientation of carbon materials on sodium storage sites and diffusion kinetics, thereby achieving controlled sodium storage. This work shows that commercial carbon fibers can serve as robust hosts for sodium deposition and enhances the theoretical understanding of how the microcrystalline structure of carbon materials relates to sodium storage properties.
Unraveling the Molecular Origin of Prey‐Wrapping Spider Silk's Unique Mechanical Properties and Assembly Process Using NMR
Authors: Chalek Kevin , Onofrei David , Aldana Julian E. , Johnson Hannah R. , Stengel Dillan , Chau Andy T. , Domingo Anikin Rae , Alcala Erik , Tsui Esther , Botello Francisco , Soni Ashana , Addison Bennett , Holland Gregory P.
Published: July 2024

Prey wrapping spider silk's unique mechanical properties are investigated confirming the silk's high degree of extensibility and superior toughness compared to other types of spider silk. For the first time, the pre‐spinning dope phase is studied in isotope‐enriched intact aciniform (AC) silk glands using solution NMR that reveals a combination of α‐helical domains linked by disordered random coil chains consistent with previously proposed “beads‐on‐a‐string” models. The model is further refined through the AlphaFold2 protein structure prediction tool. Finally, extensive magic angle spinning (MAS) solid‐state (SS) NMR data for isotopically‐enriched fibers is used to refine the structural model for AC silk from two species, A. aurantia and A. argentata. The SSNMR data shows that the AC silk fibers are highly α‐helical, coiled‐coil in structure but, also exhibit significant β‐sheet components that can be traced back to the Gly‐rich disordered linker regions in the pre‐spinning dope phase that are converted to β‐sheet structures during fiber formation. This combination of mechanical and structural characterization enhances the understanding of AC silk's liquid‐to‐solid transition and structure‐mechanics relationship. These prey wrap silk results and models will provide the basis for the design of biomimetic materials inspired by the AC spider silk system.
Core–Shell Nanostructured Assemblies Enable Ultrarobust, Notch‐Resistant and Self‐Healing Materials
Authors: Li Changchun , Yang Xin , Wang Yuyan , Liu Jize , Zhang Xinxing
Published: July 2024

Actuators based on stimulus‐responsive soft materials have attracted widespread attention due to their significant advantages in flexibility and structural adaptability over traditional rigid actuators. However, the development of fast‐actuating, mechanical robust and self‐healing actuators without compromising flexibility remains an ongoing challenge. Here, this study presents a photo‐responsive flexible actuator by incorporating core–shell liquid metal nano‐assemblies into a polyurethane matrix to construct a dynamic supramolecular interface. The nano‐assemblies are endowed with adaptive characteristics to external loading, being expected to dissipate energy via the reversible reconstruction of hydrogen bonding and deformation of nano‐assemblies. The obtained composites exhibit excellent mechanical strength (31 MPa), low modulus (2.02 MPa), high stretchability (1563.95%), autonomous self‐healing (92.5%), and NIR‐responsive actuation properties. Furthermore, the combination of high cohesive energy but fluxible nano‐liquid metal core, and strong dynamic interface not only achieves the balance of high tensile strength and high flexibility but also endows the actuators with outstanding notch‐resistant performance (fracture energy≈58.8 kJ m−2) through multiphase energy dissipation. This work provides a promising strategy for developing soft yet tough self‐healing materials in the fields of flexible robotics and artificial muscles.
A Dual‐Carbon Potassium‐Ion Capacitor Enabled by Hollow Carbon Fibrous Electrodes with Reduced Graphitization
Authors: Shi Xiaojun , Wang Huanwen , Xie Zeren , Mao Zhifei , Zhang Taoqiu , Jin Jun , He Beibei , Wang Rui , Gong Yansheng , Fan Hong Jin
Published: July 2024

The large size of K+ ions (1.38 Å) sets a challenge in achieving high kinetics and long lifespan of potassium storage devices. Here, a fibrous ZrO2 membrane is utilized as a reactive template to construct a dual‐carbon K‐ion capacitor. Unlike graphite, ZrO2‐catalyzed graphitic carbon presents a relatively disordered layer arrangement with an expanded interlayer spacing of 0.378 nm to accommodate K+ insertion/extraction. Pyridine‐derived nitrogen sites can locally store K‐ions without disrupting the formation of stage‐1 graphite intercalation compounds (GICs). Consequently, N‐doped hollow graphitic carbon fiber achieves a K+‐storage capacity (primarily below 1 V), which is 1.5 time that of commercial graphite. Potassium‐ion hybrid capacitors are assembled using the hollow carbon fiber electrodes and the ZrO2 nanofiber membrane as the separator. The capacitor exhibits a high power of 40 000 W kg−1, full charge in 8.5 s, 93% capacity retention after 5000 cycles at 2 A g−1, and a low self‐discharge rate of 8.6 mV h−1. The scalability and high performance of the lattice‐expanded tubular carbon electrodes underscores may advance the practical potassium‐ion capacitors.
Dynamic Memristors for Temporal Signal Processing
Authors: Song Fuming , Shao He , Ming Jianyu , Sun Jintao , Li Wen , Yi Mingdong , Xie Linghai , Ling Haifeng
Published: July 2024

The rapid advancement of neuromorphic computing demands innovative hardware solutions capable of efficiently mimicking the functionality of biological neural systems. In this context, dynamic memristors have emerged as promising candidates for realizing neuromorphic reservoir computing (RC) architectures. The dynamic memristors characterized by their ability to exhibit nonlinear conductance variations and transient memory behaviors offer unique advantages for constructing RC systems. Unlike recurrent neural networks (RNNs) that face challenges such as vanishing or exploding gradients during training, RC leverages a fixed‐size reservoir layer that acts as a nonlinear dynamic memory. Researchers can capitalize on their adaptable and efficient characteristics by integrating dynamic memristors into RC systems to enable rapid information processing with low learning costs. This perspective provides an overview of the recent developments in dynamic memristors and their applications in neuromorphic RC. It highlights their potential to revolutionize artificial intelligence hardware by offering faster learning speeds and enhanced energy efficiency. Furthermore, it discusses challenges and opportunities associated with integrating dynamic memristors into RC architectures, paving the way for developing next‐generation cognitive computing systems.
Cp*Rh(III)‐Catalyzed Divergent Synthesis of N‐Heterocycles with N‐Methoxyindoleamides and Isoxazolones
Authors: Shen Dan‐Ting , Zou Wen‐Xuan , Chen Shao‐Yong , Xiao Lin , Hu Qiong , Song Jia‐Lin , Liu Xu‐Ge , Zhang Shang‐Shi
Published: July 2024

A method for synthesizing pyrimido[1,2‐a]indol‐4‐ol heteroarenes via a Cp*Rh(III)‐catalyzed cascade C−H activation/annulation strategy employing N‐methoxyindoleamides and isoxazolones is developed. Also, a framework of 3‐methoxy‐2,3‐dihydro‐[1,3,5]triazino[1,2‐a]indole‐4,10‐dione was successfully synthesized via a Cp*Rh‐catalyzed C−H activation/annulation/oxidation reaction between N‐(methyloxy)‐1H‐indole‐1‐carboxamide and isoxazolones. These reactions demonstrated the suitability of several substrates, compatibility with numerous functional groups, and mild reaction conditions. Preliminary mechanistic investigations have been completed.
Synthesis, Characterization and Biological Evaluation of 3‐Oxo‐Pyrimido[1,2‐b]indazoles
Authors: Zhang Xinyu , Zhao Xuan , Wu Die , Zhang Jingsa , Shou Yilu , Wang Xingya , Ma Yongmin , Zhu Bihong
Published: July 2024

The synthesis of substituted 3‐oxo‐pyrimido[1,2‐b]indazoles from 3‐aminoindazoles and ketones has been established. It involves one molecule of 3‐aminoindazoles and two molecules of ketones via a [3+2+1] three‐component annulation process. 3‐Oxo‐pyrimido[1,2‐b]indazoles exhibit strong yellow fluorescence in various solvents. A wide range of products have anti‐oxidant activities. Cytotoxicity studies indicate that compounds 3 a, 3 aa and 3 ab have obvious effects on both HCT116 and A549 cancer cell lines.
Ozanimod and Prazosin as Inhibitor of bonding SARS‐CoV‐2 spike protein and the ACE2 enzyme: Molecular Dynamics and Molecular Docking Study of Potential Drugs
Authors: Hosseinzadeh Maryam , Shidpour Reza , Rajabi Mohammad
Published: July 2024

To develop the drugs as a second line of preventing a serious form of illness, blocking the interaction between a receptor‐binding domain (RBD) in the SARS‐CoV‐2 S‐protein (spike protein) with human ACE2 (Angiotensin converting enzyme 2) can potentially prevent SARS‐CoV‐2 S‐protein from interacting with host cells. In this research, 20 drug compounds are examined using docking to identify potential drugs that can bind at the common level of the RBD‐ACE2 complex and compared the results with two standard drugs offered (Favipiravir, Arbidol). Among 20 drugs, Ozanimod and Prazosin are selected as the best drug compounds by reviewing the docking scores and drug interaction with the active position of RBD‐ACE2. The results of molecular dynamics simulation showed that Ozanimod with binding energy of −14.24 kcal mol−1 has a higher binding capability than Prazosin with binding energy of −9.55 kcal mol−1 to block the interaction between spike protein RBD and human ACE2 enzyme. Ozanimod effectively binds to the S‐protein RBD and inhibits residues critical to the spike and ACE2 protein interaction. This drug compound is expected to be a potentially effective inhibitor of the interaction between the S‐ RBD and the human ACE2 enzyme.
Study on the Diffusion Law of Shield Filling Grouting Slurry Based on VOF‐Multiphase Flow Considering Radial Seepage
Authors: Song Shuguang , Lu Wangtong
Published: July 2024

Synchronous grouting technology is a crucial aspect of shield tunnel construction. However, understanding the mechanism of slurry diffusion during this process is challenging due to its complexity and invisibility. Existing theoretical models often oversimplify the grouting process and do not account for multi‐stage diffusion mechanisms. By considering the radial penetration of slurry and viewing the diffusion process as the formation of annular pancakes through circumferential filling, a 3D diffusion numerical model is established using the volume of fluid (VOF)‐multiphase flow model in Fluent software. The model's validity is confirmed through calculations based on theoretical formulas and monitoring data from engineering examples. This study uncovers the patterns of slurry diffusion and examines how factors like porosity, grouting pressure, and slurry density impact diffusion radius and segment stress. The findings of this research provide a crucial theoretical foundation for shield synchronous grouting construction.
The Stabilization Effect of Agmatine‐Salicylate Ionic Liquids on PARP‐1 for Parkinson's Disease: A Perspective from DFT and MD Simulations
Authors: Priyankha Sridhar , Prakash Muthuramalingam
Published: July 2024

The pathogenesis of Parkinson's disease (PD), a chronic degenerative disorder, is influenced by poly(ADP‐ribose) polymerase‐1 (PARP‐1) since its activation is a prerequisite in dopaminergic neuronal cell death. The biocompatible agmatine‐salicylate ionic liquid (i.e., [Agm][Sal2] IL) has shown promising anticancer and non‐cytotoxic characteristics. The stability of the complexes is inferred to be significantly influenced by the water‐mediated hydrogen bonding (H‐bonding) interactions of cations and anions with aromatic amino acids in the presence and absence of water molecules, as established by density functional theory (DFT) calculations of the [Agm]2+ and [Sal]− ions. To identify the structural stability of PARP‐1 in an IL medium, a series of concentrations (mole fraction 0.20–1.00) of ILs with PARP‐1 using molecular dynamics (MD) simulations are studied for 200 ns. While the oxygen atoms in the ─COO− group of [Sal]− anions established strong H‐bonding interactions with the water molecules, the dicationic [Agm]2+ cations formed H‐bonding interactions with the residues of PARP‐1. It is concluded through various analyses that PARP‐1 maintains its structural stability at 0.60–0.80 mole fractions of ILs in an aqueous medium. Thus, this finding signifies [Agm][Sal2] IL as an efficient PARP‐1 stabilizer; with further in vitro studies this IL can aid in the treatments for PD.
Developing dual‐state ultra‐efficient emissive carbon dots as internal and external artificial antenna of chloroplasts to enhance plant‐photosynthesis
Authors: Zhao Shijie , Wang Hongyang , He Jiuxing , Dong Linlin , Xie Tianyou , Luo Yang , Li Jie , Lartey Patrick Osei , Guo Kunpeng , Liu Jialei
Published: July 2024

Introducing fluorescent nanomaterials as artificial antennas of chloroplasts offers a promising approach to enhancing light harvesting in photosynthesis. However, this technology is limited by the dependence of the fluorescence efficiency of nanomaterials on dispersed states that cannot enable nanomaterials inside and outside leaves to play an antenna role. Here, we developed solution and solid dual‐state ultra‐efficient blue emissive carbon dots (DuB2‐CDs) by regulating the content of graphitic‐N, surface hydroxyl groups. and C–Si bonds based on a four‐component microwave synthesis. The as‐prepared DuB2‐CDs showed intense blue emission in aqueous solution and solid state, with absolute photoluminescence quantum yields of 84.04% and 95.69%, respectively. These features guaranteed that the internal (DuB2‐CDs infiltrating the mesophyll system) and external (DuB2‐CDs remaining on the surface of leaves) artificial antennas can simultaneously enhance the solar energy utilization efficiency of chloroplasts. Compared with the control groups without antenna use and internal antenna use only, the foliar application of DuB2‐CDs substantially enhanced the electron‐transport rate, net photosynthesis rate, psbA gene expression, NADPH production, and other plant physiological parameters of living plant during photosynthesis. This work provided a promising strategy for realizing dual‐state ultra‐efficient emissive CDs while maximizing living plant‐photosynthesis augmentation.
Multimerization of TREM2 is impaired by Alzheimer's disease–associated variants
Authors: Dean Hunter B. , Greer Rory A. , Yang Shan‐Zhong , Elston Daniel S. , Brett Thomas J. , Roberson Erik D. , Song Yuhua
Published: July 2024

INTRODUCTION

The immune receptor triggering receptor expressed on myeloid cells 2 (TREM2) is among the strongest genetic risk factors for Alzheimer's disease (AD) and is a therapeutic target. TREM2 multimers have been identified in crystallography and implicated in the efficacy of antibody therapeutics; however, the molecular basis for TREM2 multimerization remains poorly understood.

METHODS

We used molecular dynamics simulations and binding energy analysis to determine the effects of AD‐associated variants on TREM2 multimerization and validated with experimental results.

RESULTS

TREM2 trimers remained stably bound, driven primarily by salt bridge between residues D87 and R76 at the interface of TREM2 units. This salt bridge was disrupted by the AD‐associated variants R47H and R98W and nearly ablated by the D87N variant. This decreased binding among TREM2 multimers was validated with co‐immunoprecipitation assays.

DISCUSSION

This study uncovers a molecular basis for TREM2 forming stable trimers and unveils a novel mechanism by which TREM2 variants may increase AD risk by disrupting TREM2 oligomerization to impair TREM2 normal function.

Highlights

Triggering receptor expressed on myeloid cells 2 (TREM2) multimerization could regulate TREM2 activation and function.

D87–R76 salt bridges at the interface of TREM2 units drive the formation of stable TREM2 dimers and trimers.

Alzheimer's disease (AD)–associated R47H and R98W variants disrupt the D87–R76 salt bridge.

The AD‐associated D87N variant leads to complete loss of the D87–R76 salt bridge.
A Multielectron and High‐Potential Spirobifluorene‐Based Posolyte for Aqueous Redox Flow Batteries
Authors: Pang Shuai , Li Lu , Ji Yunlong , Wang Pan
Published: July 2024

The rising energy demand driven by human activity has posed pressing challenges in embracing renewable energy, necessitating advances in energy storage technologies to maximize their utilization efficiency. Recent studies in aqueous organic redox flow batteries have focused primarily on the development of organic negative electrolytes, while the progress in organic positive electrolytes remains constrained by limitations in their redox potentials and effective electron concentrations. Herein, we report a spatially twisted chlorinated spirobifluorene ammonium salts (CSFAs), created through an unexpected green chlorination‐protection pathway during the initial cycling in the flow battery cell, utilizing chloride ions from counterions in aqueous solution. The chlorinated, nonplanar spiral structure of CSFAs possesses a one‐step four‐electron transfer electrochemical property and offers exceptional resistance to nucleophilic attacks, exhibiting an unprecedented redox potential as high as 1.05 V (vs. SHE). A full redox flow battery based on CSFA‐Cl (chloride ions as the counter ions) with 1.4 M electron concentration achieved an average coulombic efficiency exceeding 99.4 % and a capacity utilization reaching 95 % of the four‐electron capacity for a stable cycling over 250 cycles (~22 days). The present work exemplifies the use of side reactions to develop new redox species, which can be extended to create more structurally versatile energy storage materials.
Controlling the asphaltene precipitation behaviors by changing the position and number of nitrogen in the aromatic heterocyclic pendant of polymers with the assistance of DFT calculations
Authors: Jia Lingli , Sun Xinjie , Wei Xingguo , Li Xinyuan , Xi Zuojia , Pi Yanfu , Xu Jun
Published: July 2024

As the largest component in crude oil, asphaltenes are apt to settle out and result in the blockage of pipeline during production and transportation, which largely reduces the safety and economic benefits. In this study, a series of poly(maleic anhydride‐octadecene)s (PMO) amidated by pyrimidine (MD), pyrazine (BQ), pyrazole (BZ), triazole (3DZ), triazine (6J3Q), phenyl triazine (6B3Q) and pyrazolo pyridine (ZBD) were synthesized. The interaction energies between the different polymers and asphaltene were calculated by using density functional theory (DFT). It shows that the greater the number of nitrogen‐containing groups and rings, the higher the interaction energy. Moreover, the position of the nitrogen on the aromatic ring also impacts the interaction energy. The interaction energy between asphaltene and polymer with adjacent N (PMO‐BZ) is larger than that with para‐N (PMO‐BQ) and interstitial N (PMO‐MD). In addition, the performance of polymers on asphaltene precipitation from model oil and crude oil is explored by UV–Vis spectroscopy, turbidity, dynamic light scattering (DLS) and rheological methods. The performance of polymers follows the sequence of PMO‐BZ > PMO‐6J3Q > PMO‐BQ > PMO‐MD > PMO‐6B3Q > PMO‐ZBD, which is not consistent with the change of interaction energy. Apparently, the efficiency of the polymer increases and then declines with the increase of interaction energy. Notably, the polymer (PMO‐BZ) containing monocyclic ring with adjacent N increased the IPP of asphaltenes from 0.363 to 0.800 and reduced the particle size from 1527.2 to 99.7 nm. The interaction energies of PMO‐BZ and PMO‐6J3Q with asphaltene are in the range of 15.87–17.04 KJ/mol, and the polymers with interaction energies in this range are more effective on asphaltene inhibition than the others. Consequently, the interaction energies obtained from DFT calculations can be used to guide the design and synthesis of polymers with nitrogen‐containing heterocyclic pendant for asphaltene inhibition.