bluuebunny/crossref_metadata_2025_split huggingface dataset:
Non‐Equal Ratio Cocrystal Engineering to Improve Charge Transport Characteristics of Organic Semiconductors: A Case Study on Indolo[2,3‐a]carbazole
Authors: Guo Junfeng , Zeng Yan , Zhen Yonggang , Geng Hua , Wang Zongrui , Yi Yuanping , Dong Huanli , Hu Wenping 
Published: May 2022

AbstractRare studies of cocrystal engineering have focused on improving carrier mobility of organic semiconductors mainly because of the generation of ambipolarity, the alteration of the charge carrier polarity or the reduction of electronic couplings. Herein, we utilize indolo[2,3‐a]carbazole (IC) as the model compound and 2,6‐diphenylanthraquinone (DPAO) and 9‐fluorenone (FO) as the coformers to construct IC2‐DPAO and IC‐FO cocrystals with 2 : 1 or 1 : 1 ratios, respectively, through hydrogen bonds and donor–acceptor interactions. Interestingly, the more appropriate packing structure, possessing not only enhanced electronic couplings but also increased intermolecular distances, is achieved in IC2‐DPAO, which shows an improved carrier mobility of 0.11 cm2 V−1 s−1 by four orders of magnitude relative to the IC crystal. These results suggest that non‐equal ratio cocrystal engineering opens up the possibility to develop organic semiconductors with enhanced charge transport behaviors.
Delicate and Fast Photochemical Surface Modification of 2D Photoresponsive Organosilicon Metal–Organic Frameworks
Authors: Yuan Baoling , Gou Gaozhang , Fan Tao , Liu Mingxian , Ma Yunsheng , Matsuda Ryotaro , Li Liangchun 
Published: May 2022

AbstractPhotoresponsive arylsilanes have been fascinating molecules for decades because of their unique photophysical characteristics and surface chemistry. Here we report the synthesis and fabrication of a crystalline two‐dimensional trisilyl metal–organic framework (TSiMOF) orderly installed with the classical photoresponsive hexamethyltrisilane groups on the surface. Irradiated by UV light under air in minutes the fluorescence of the TSiMOF is turned on simultaneously with an intriguing surface transformation from superhydrophobic to hydrophilic. Thus, multifarious luminescent and hydrophilic patterns including logos, characters and Quick Response codes, etc. with good resolution are readily generated on the facilely fabricated TSiMOF film. The mechanism of this transformation is revealed by control experiments that the superficial trimethylsilyl groups suffering photochemical oxidation have been converted to hydroxyl groups.
Confinement‐Induced Selectivities in Gold(I) Catalysis—The Benefit of Using Bulky Tri‐(ortho‐biaryl)phosphine Ligands
Authors: Muratov Karim , Gagosz Fabien 
Published: May 2022

AbstractThe confinement of a catalytic site is an efficient strategy to control a reaction and modulate its selectivity. In the present work, a new class of structurally simple and easily accessible bulky tri‐(ortho‐biaryl)phosphine ligands were accessed, and their gold(I) complexes synthesized. Their X‐ray diffraction analysis and the comparative evaluation of their VBur% and G steric parameters against a series of gold complexes commonly employed in catalysis demonstrated their confined nature. Despite their notable steric congestion, these complexes exhibited remarkable catalytic activities and unusual selectivities, both in nature and level, that make them unique in the field of synthetic homogeneous gold catalysis.
Tunable and improved antiproliferative activity of Pt (II)‐based organometallics bearing alkynyls and 1,2,3‐triazole moieties
Authors: Chakraborty Arnab , Jaiswal Chitra , Hassan Atikur , Kumar Saurabh , Singh Khushwant , Mandal Biman B. , Das Neeladri 
Published: May 2022

AbstractSynthesis and characterization of a set of four Pt (II)‐based organometallic compounds (7–10) are being described. These molecules are unique since each of these contain three biologically active structural motifs, in the form of a pyrazine ring that connects a Pt‐alkynyl and a triazole ring. These organoplatinum molecules have been characterized using multinuclear nuclear magnetic resonance (NMR) (1H, 13C{1H}, and 31P{1H}), Fourier transform infrared spectroscopy (FT–IR), and mass spectrometry (MS). Additionally, the antiproliferative activities of 7–10 were probed against human triple‐negative breast cancer cells (MDA‐MB‐231) and normal human dermal fibroblast cells (HDF).
Synthesis and characterization of waste polyethylene reinforced modified castor oil‐based polyester biocomposite
Authors: Aydoğmuş Ercan , Dağ Mustafa , Yalçın Zehra Gülten , Arslanoğlu Hasan 
Published: May 2022

AbstractIn this research, modified castor oil (MCO)‐based biocomposite has been synthesized and its structure is strengthened with waste polyethylene (PE) reinforcement. Both the petrochemical raw material used is reduced by 12 wt% and a new environmentally friendly biocomposite is produced using waste PE. Considering some thermophysical properties of the obtained biocomposite, experimental working conditions, and composition ratios have been optimized with response surface methodology (RSM). The chemical bond structure of the biocomposite has been investigated by Fourier transform infrared spectrophotometer, thermal decomposition behavior by thermogravimetric analysis, and surface morphology by scanning electron microscopy. According to the results obtained, the density and hardness of the biocomposite synthesized by the addition of MCO to unsaturated polyester (UP) decreases, and its thermal conductivity and thermal stability increase. The thermal decomposition kinetics of the biocomposite is also modeled with the newly improved hyperbolic function equation. The relationship between conversion rate and the temperature has been determined by the new model with a high correlation coefficient (R2 = 0.9985) and low‐error functions (SST = 0.0096, RMSE = 0.0285, χ2 = 0.0037). Effective and efficient use of MCO, UP, methyl ethyl ketone peroxide, and cobalt octoate in the production process has provided an economical and steady the biocomposite. Evaluation of experimental data with both RSM and artificial neural networks raises the reliability of the model results.
Sex‐specific effects of PET‐MPs onDrosophilalifespan
Authors: Liang Boying , Zhang Dake , Liu Xingyou , Xu Yifan , Tang Hao , Li Yan , Shen Jie 
Published: May 2022

AbstractIn recent years, as an emerging pollutant, microplastic (MPs) pollution is gradually becoming a research hotspot. MPs are ubiquitous in the entire ecological environment. Organisms can be exposed to MPs via inhalation or ingestion. In view of the widespread of MPs pollution, the impact of MPs on biology should be further investigated. In previous experiments, we have conducted research on the physiology ofDrosophilaexposed to polyethylene terephthalate microplastics (PET‐MPs). However, will the lifespan ofDrosophilabe affected under long‐term PET‐MPs exposure? The analysis of variance analysis of our experimental results indicates that there are significant differences between males and females,F(1, 895) = 68.19,p < 0.001, between PET‐MPs concentration,F(3, 895) = 8.11,p < 0.001. There are also significant interactions between sex and MP concentration,F(3, 895) = 4.00,p < 0.01. For Cox and log‐rank test, 1 g/L of PET‐MPs prolongs the lifespan of male flies. The reason for this phenomenon may be the hormesis effect.
Comparative Genetic Analysis of Psoriatic Arthritis and Psoriasis for the Discovery of Genetic Risk Factors and Risk Prediction Modeling
Authors: Soomro Mehreen , Stadler Michael , Dand Nick , Bluett James , Jadon Deepak , Jalali‐najafabadi Farideh , Duckworth Michael , Ho Pauline , Marzo‐Ortega Helena , Helliwell Philip S. , Ryan Anthony W. , Kane David , Korendowych Eleanor , Simpson Michael A. , Packham Jonathan , McManus Ross , Gabay Cem , Lamacchia Céline , Nissen Michael J. , Brown Matthew A. , Verstappen Suzanne M. M. , Van Staa Tjeerd , Barker Jonathan N. , Smith Catherine H. ,   the BADBIR Study Group,   the BSTOP study group, FitzGerald Oliver , McHugh Neil , Warren Richard B. , Bowes John , Barton Anne 
Published: May 2022

ObjectivesPsoriatic arthritis (PsA) has a strong genetic component, and the identification of genetic risk factors could help identify the ~30% of psoriasis patients at high risk of developing PsA. Our objectives were to identify genetic risk factors and pathways that differentiate PsA from cutaneous‐only psoriasis (PsC) and to evaluate the performance of PsA risk prediction models.MethodsGenome‐wide meta‐analyses were conducted separately for 5,065 patients with PsA and 21,286 healthy controls and separately for 4,340 patients with PsA and 6,431 patients with PsC. The heritability of PsA was calculated as a single‐nucleotide polymorphism (SNP)–based heritability estimate (h2SNP) and biologic pathways that differentiate PsA from PsC were identified using Priority Index software. The generalizability of previously published PsA risk prediction pipelines was explored, and a risk prediction model was developed with external validation.ResultsWe identified a novel genome‐wide significant susceptibility locus for the development of PsA on chromosome 22q11 (rs5754467;P = 1.61 × 10−9), and key pathways that differentiate PsA from PsC, including NF‐κB signaling (adjustedP = 1.4 × 10−45) and Wnt signaling (adjustedP = 9.5 × 10−58). The heritability of PsA in this cohort was found to be moderate (h2SNP = 0.63), which was similar to the heritability of PsC (h2SNP = 0.61). We observed modest performance of published classification pipelines (maximum area under the curve 0.61), with similar performance of a risk model derived using the current data.ConclusionKey biologic pathways associated with the development of PsA were identified, but the investigation of risk classification revealed modest utility in the available data sets, possibly because many of the PsC patients included in the present study were receiving treatments that are also effective in PsA. Future predictive models of PsA should be tested in PsC patients recruited from primary care.
Existence and controllability of second‐order nonlinear retarded integro‐differential systems with multiple delays in control
Authors: Haq Abdul 
Published: May 2022

AbstractThis work analyzes the existence and exact controllability of nonlinear second‐order retarded integro‐differential equations involving delays in control. Making use of fixed point principle and cosine family we determine the existence of solutions. Then, under some assumptions, we show that the controllability of the associated linear system without delay implies the controllability of the associated linear delay system and the actual system by applying an iterative technique. To illustrate the results, we introduce an example.
State space construction for continuous time transfer function matrices via Nerode equivalence
Authors: Liu Jing , French Mark , Fang Li‐Ping 
Published: May 2022

AbstractIn this paper, we show that a minimal state space realization in Jordan canonical form for linear multivariable continuous‐time systems described by rational transfer function matrices could be obtained in a natural and basic way by using the concept of Nerode equivalence. While the minimal state space realization is known, the contribution of this note is to provide an alternative realization procedure which is directly introduced in a simple and self‐contained manner. Both scalar and multivariable cases in the continuous‐time setting are discussed. The presentation also provides a concrete construction of rational vector function with preassigned poles to interpolate any 2‐norm bounded analytical vector function in the open left‐half of the complex plane. The basic idea of Nerode equivalence is that the state can be identified with a corresponding equivalence class of inputs. For a linear finite dimensional time‐invariant continuous‐time system, the zero state is identified with the kernel of certain Hankel operator. This characterization via Nerode equivalence class sheds light on the construction of state for general nonlinear input–output systems.
Parametric design of functional observer for second‐order linear time‐varying systems
Authors: Gu Da‐Ke , Sun Li‐Song , Liu Yin‐Dong 
Published: May 2022

AbstractThis note constructs a functional observer for second‐order linear time‐varying (SOLTV) systems under framework of second‐order systems. Based on the assumption that the SOLTV system is observable, sufficient conditions for the existence of a second‐order functional observer are proposed. Combined with the solution of generalized Sylvester equation (GSE), the completely parameterized expressions of coefficient matrices of functional observer are proposed, which includes the free parameters representing degrees of freedom, and can be utilized to achieve some additional performance. Further, the design procedure is put forward, whose validity is verified through an example.
Altered hippocampal volume and functional connectivity in patients with Cushing's disease
Authors: Li Chuqi , Zhang Yanyang , Wang Wenxin , Zhou Tao , Yu Xinguang , Tao Hong 
Published: May 2022

AbstractIntroductionStress‐related brain disorders can be associated with glucocorticoid disturbance and hippocampal alteration. However, it remains largely unknown how cortisol affects the structure and function of hippocampus. Cushing's disease (CD) provides a unique “hyperexpression model” to explore the effects of excessive cortisol on hippocampus as well as the relation between these effects and neuropsychological deficits.MethodsWe acquired high‐resolution T1‐weighted and resting‐state functional magnetic resonance imaging in 47 CD patients and 53 healthy controls. We obtained the volume and functional connectivity of the hippocampal rostral and caudal subregions in both groups. Relationships between hippocampal alterations, neuroendocrine, and neuropsychological assessments were identified.ResultsRelative to control subjects, the CD patients had smaller volumes of all four hippocampal subregions. Furthermore, whole brain resting‐state functional connectivity analyses with these four different hippocampal regions as seeds revealed altered hippocampal functional connectivity with high‐order networks, involving the DMN, frontoparietal, and limbic networks in CD patients. The intrinsic hippocampal functional connectivity was associated with the quality of life of the CD patients.ConclusionsOur findings elucidate the cumulative effect of excess cortisol on the morphology and function of hippocampus and reinforce the need for effective interventions in stress‐related brain disease to halt potential hippocampal damage.
Epidemiological profile and clinical characteristics of 491 Brazilian patients with neurofibromatosis type 1
Authors: Darrigo Junior Luiz Guilherme , Ferraz Victor Evangelista de Faria , Cormedi Marina Candido Visontai , Araujo Luissa Hikari Hayashi , Magalhães Mariana Prado Silva , Carneiro Rafaella Curis , Sales Luis Henrique Nunes , Suchmacher Mendel , Cunha Karin Soares , Filho Aguinaldo Bonalumi , Azulay David Rubem , Geller Mauro 
Published: May 2022

AbstractBackgroundNeurofibromatosis type 1 (NF1) is a chronic and progressive autosomal dominant genetic and sporadic disease characterized by cutaneous and neurological abnormalities. Plexiform neurofibroma (PN), a significant cause of clinical complications in NF‐1, is a benign tumor of the peripheral nerve sheath that involves multiple nerve fascicles. Although there is an important number of patients who are affected by NF1 in Brazil, there is little data on the behavior of the disease in the national literature as well as in other low‐ and middle‐income countries.MethodsWe performed a retrospective analysis of 491 patients with NF1 followed at two reference centers in Brazil.ResultsApproximately 38% of patients had PNs, resulting in reduced life quality. The median patient age with PNs was 30 years (range: 6 to 83 years). Head and neck, and extremity were the main affected locations with 35.8 and 30.6%, respectively. PNs were classified as asymptomatic in 25.1% of patients, while 52.5% presented symptomatic and inoperable tumors. The most common manifestations related to PNs were disfigurement and orthopedic involvement. Twenty patients developed neoplasms and ten (50%) presented with malignant peripheral nerve sheath tumors (MPNST). The prevalence of MPNST in our study was 2.9%.ConclusionsPatients with NF1 experience clinically significant morbidity, especially when it is associated with PN. Though there are many patients affected by NF1 in Brazil and other low‐ and middle‐income countries, there is little data available in the corresponding literature. Our results are comparable to the previous results reported from higher‐income countries and international registries.
Utility of coronary orbital atherectomy with guide‐extension system for distally located undilatable in‐stent restenosis: A case report
Authors: Yamamoto Hiroyuki , Sawada Takahiro , Takaya Tomofumi , Kawai Hiroya 
Published: May 2022

AbstractOrbital atherectomy (OA) may be effective in managing undilatable in‐stent restenosis (ISR) despite off‐label indications. We demonstrated that optical frequency domain imaging (OFDI)‐guided OA, with a guide‐extension system was effective even in distally located, undilatable ISR. However, OFDI revealed that inter‐struts calcified neoatherosclerosis remained a challenging issue.
Consequences of Intrapore Liquids on Reactivity, Selectivity, and Stability for Aldol Condensation Reactions on Anatase TiO2 Catalysts
Authors: Kadam Shashikant A. , Hwang Andrew , Iglesia Enrique 
Published: May 2022

AbstractThis study provides evidence and mechanistic interpretations for the significant consequences of intrapore non‐polar liquids on acetone aldol condensation turnover rates, selectivity to primary dimer products, and catalyst stability for reactions at Lewis acid‐base site pairs on TiO2 surfaces. These non‐polar liquids confer such benefits through the preferential stabilization of transition states (TS) for adsorption (“entry”) and desorption (“exit”) steps, which place their respective reactants or products within a solvating outer sphere environment. The extent to which non‐polar fluids (n‐heptane) form an intrapore liquid phase within TiO2 voids was obtained from N2 uptakes using established formalisms that consider the different molal volume, surface tension, and volatility between N2 and n‐heptane. Acetone condensation rates are limited by C−H activation, an “entry” step that forms bound prop‐1‐en‐2‐olates via a TS stabilized by intrapore liquids, leading to higher aldol condensation turnover rates as n‐heptane pressure increases and active TiO2 surfaces become increasingly immersed within a non‐polar liquid phase. These liquids solvate the late TS structures that mediate the desorption of primary C6 condensation products even more effectively than those involved in prop‐1‐en‐2‐olate formation or in nucleophilic attack events that later form C−C bonds. Such preferential solvation favors desorption over C−C coupling events, thus disfavoring the formation of larger oligomers that become stranded at active sites, thus leading to much slower deactivation. Moreover, solvation by non‐polar liquids also leads to C6 alkanones as the sole products formed in a single surface sojourn. These effects of a non‐polar dense phase circumvent the inherent stability, reactivity, and selectivity hurdles that have precluded practical aldol condensation catalysis on Lewis acid‐base pairs at oxide surfaces; these consequences are demonstrated here for TiO2 catalysts, acetone aldol condensation reactions, and n‐heptane as the non‐polar liquid but through strategies, concepts, and mechanistic features that extend to other systems. More generally, these observations and their mechanistic origins demonstrate how a contacting liquid preferentially solvates TS structures for elementary steps that involve either reactants arriving from or products entering into an outer sphere environment that contains a dense non‐polar phase.
4‐Fluorophenylsulfonylacetonitrile as an Electrolyte Additive for Improving the High‐Voltage Performance of LiNi0.83Co0.11Mn0.06O2 Cathode Batteries
Authors: Wu Qian , Li Jianmei , Sheng Yu , Tong Qingsong 
Published: May 2022

AbstractHigh‐nickel ternary materials have attracted attention as advanced cathode materials for lithium‐ion batteries (LIBs) owing to their high energy density and low cost. However, the side reactions between carbonate‐based electrolytes and cathode materials under high voltages remain the most significant obstacle to the further application of high‐nickel LIBs. To develop superior LIBs, 4‐fluorobenzenesulfonylacetonitrile (FPSAN) is proposed as a new electrolyte additive to enhance the safety of high‐nickel LIBs. The results demonstrate that the easily decomposed FPSAN can form a protective film on the cathode surface, thereby improving the cycling stability and rate performance of the Li/LiNi0.83Co0.11Mn0.06O2 half‐cells. The FPSAN additive can also maintain the spinel shape of the LiNi0.83Co0.11Mn0.06O2 cathode particles. These results indicate that the FPSAN electrolyte additive can facilitate the application of high‐performance LiNi0.83Co0.11Mn0.06O2 cells.
Direct and Asymmetric Aldol Reactions of N‐Azidoacetyl‐1,3‐thiazolidine‐2‐thione Catalyzed by Chiral Nickel(II) Complexes. A New Approach to the Synthesis of β‐Hydroxy‐α‐Amino Acids
Authors: Teloxa Saul F. , Mellado‐Hidalgo Miguel , Kennington Stuart C. D. , Romea Pedro , Urpí Fèlix , Aullón Gabriel , Font‐Bardia Mercè 
Published: May 2022

AbstractA direct and asymmetric triisopropylsilyltrifluoromethanesulfonate (TIPSOTf) mediated aldol reaction of N‐azidoacetyl‐1,3‐thiazolidine‐2‐thione with aromatic aldehydes catalyzed by a chiral nickel(II)‐Tol‐BINAP complex has been developed (BINAP=2,2’‐bis(diphenylphosphino)‐1,1’‐binaphthyl). The catalytic protocol gives the corresponding anti α‐azido‐β‐silyloxy adducts with outstanding stereocontrol and in high yields. Theoretical calculations account for the stereochemical outcome of the reaction and lay the foundations for a mechanistic model. In turn, the easy removal of the thiazolidinethione yields a wide array of enantiomerically pure derivatives in a straightforward and efficient manner. Such a noteworthy character of the heterocyclic scaffold together with the appropriate manipulation of the azido group open a new route to the synthesis of di‐ and tripeptide blocks containing a β‐aryl‐β‐hydroxy‐α‐amino acid.