bluuebunny/crossref_metadata_2025 huggingface dataset:
Cobalt‐Catalysed Asymmetric Addition and Alkylation of Secondary Phosphine Oxides for the Synthesis of P‐Stereogenic Compounds
Authors: Wu Zeng‐Hua , Cheng An‐Qi , Yuan Meng , Zhao Ya‐Xuan , Yang Huai‐Lan , Wei Li‐Hua , Wang Huai‐Yu , Wang Tao , Zhang Zunting , Duan Wei‐Liang
Published: November 2021

The catalytic asymmetric synthesis of P‐chiral phosphorus compounds is an important way to construct P‐chiral ligands. Herein, we report a new strategy that adopts the pyridinyl moiety as the coordinating group in the cobalt‐catalysed asymmetric nucleophilic addition/alkylation of secondary phosphine oxides. A series of tertiary phosphine oxides were generated with up to 99 % yield and 99.5 % ee, and with broad functional‐group tolerance. Mechanistic studies reveal that (R)‐secondary phosphine oxides preferentially interact with the cobalt catalysts to produce P‐stereogenic compounds.
Solid‐Phase‐Supported Chemoenzymatic Synthesis of a Light‐Activatable tRNA Derivative
Authors: Blümler Anja , Schwalbe Harald , Heckel Alexander
Published: November 2021

Herein, we present a multi‐cycle chemoenzymatic synthesis of modified RNA with simplified solid‐phase handling to overcome size limitations of RNA synthesis. It combines the advantages of classical chemical solid‐phase synthesis and enzymatic synthesis using magnetic streptavidin beads and biotinylated RNA. Successful introduction of light‐controllable RNA nucleotides into the tRNAMet sequence was confirmed by gel electrophoresis and mass spectrometry. The methods tolerate modifications in the RNA phosphodiester backbone and allow introductions of photocaged and photoswitchable nucleotides as well as photocleavable strand breaks and fluorophores.
Five‐Fold Symmetric Pentaindolo‐ and Pentakis(benzoindolo)Corannulenes: Unique Structural Dynamics Derived from the Combination of Helical and Bowl Inversions
Authors: Kise Koki , Ooi Shota , Saito Hayate , Yorimitsu Hideki , Osuka Atsuhiro , Tanaka Takayuki
Published: November 2021

Peripherally π‐extended corannulenes bearing quintuple azahelicene units, 10 and 11, were prepared and their dynamic behaviors were studied experimentally and theoretically. The fused corannulenes were synthesized from sym‐pentabromocorannulene in three steps. X‐Ray diffraction analysis for 10 displayed a conformer possessing a P(M) bowl chirality and a PPMPM (PMPMM) helical chirality, which was found to be the most stable conformer(s). Variable‐temperature NMR measurements of 10 and 11 revealed that their structural isomers can be interconvertible in solution, depending on the steric congestion around the helical scaffolds. Automated search for conformers in the equilibrium and transition states by Artificial Force Induced Reaction (AFIR) method revealed their interconversion networks, including bowl‐inversion and helical‐inversion. This analysis indicated that the co‐existing corannulene and azahelicene moieties influence the conformational dynamics, which leads to mitigation of the activation energy barriers for isomerization.
A Selective and General Cobalt‐Catalyzed Hydroaminomethylation of Olefins to Amines
Authors: Yang Ji , Delolo Fábio G. , Spannenberg Anke , Jackstell Ralf , Beller Matthias
Published: November 2021

A new cobalt catalyst is presented for the domino hydroformylation‐reductive amination reaction of olefins. The optimal Co‐tert‐BuPy‐Xantphos catalyst shows good to excellent linear‐to‐branched (n/iso) regioselectivity for the reactions of aliphatic alkenes with aromatic amines under mild conditions. This system is far more selective than traditional cobalt(I) catalysts and even better than most known rhodium catalysts.
Effective chiral pool synthesis of both enantiomers of the TRPML inhibitor trans‐ML‐SI3
Authors: Kriegler Katharina , Leser Charlotte , Mayer Peter , Bracher Franz
Published: November 2021

Two independent chiral pool syntheses of both enantiomers of the TRPML inhibitor, trans‐ML‐SI3, were developed, starting from commercially available (1S,2R)‐ and (1R,2S)‐configured cis‐2‐aminocyclohexanols. Both routes lead to the target compounds in excellent enantiomeric purity and good overall yields. For the most attractive (−)‐trans‐enantiomer, the R,R‐configuration was identified by these unambiguous syntheses, and the results were confirmed by single‐crystal X‐ray structure analysis. These effective synthetic approaches further allow flexible variation of prominent residues in ML‐SI3 for future in‐depth analysis of structure–activity relationships as both the piperazine and the N‐sulfonyl residues are introduced into the molecule at late stages of the synthesis.
The mental health of adolescents in England: How does it vary during their time at school?
Authors: Jerrim John
Published: November 2021

The wellbeing of young people has become an important education policy issue, with suggestions that mental health problems amongst young people have increased in recent years. Experiences at school are thought to be a key factor contributing to mental ill‐health amongst adolescents. Yet surprisingly, little is known about how mental health outcomes vary across school year groups, independent of the effects of age. This article contributes new evidence on this issue, drawing upon large‐scale health data from England. We find substantial growth in mental health problems as young people progress through secondary school. Yet this seems to be driven by the effects of age, rather than due to movement into more senior school year groups. We consequently conclude that evidence of a direct link between school year group and young people’s mental health remains relatively weak.
Confined Cobalt on Carbon Nanotubes in Solvent‐free Aerobic Oxidation of Ethylbenzene: Enhanced Interfacial Charge Transfer
Authors: Su Yongzhao , Chen Zhicheng , Huang Jiangnan , Wang Hongjuan , Yu Hao , Zhang Qiao , Cao Yonghai , Peng Feng
Published: November 2021

Aerobic oxidation of hydrocarbons yielding corresponding oxygenated products is one of the most important chemical processes. In current work, carbon nanotubes supported encapsulated cobalt nanoparticles with carbon layers (Co@C/CNTs) were synthesized and utilized as catalysts in the oxidation of ethylbenzene (EB) in the liquid phase, exhibiting high catalytic performance. The synergistic effect between Co@C and CNTs played the vital role on facilitating the decomposition of peroxides to enhance the overall activity. The inadequate covered Co@C on CNTs surface were considered as catalytic sites. Density functional theory revealed that the exist of Co nanoparticles could improve the interaction between the catalyst and intermediate free radicals, which were significant for EB oxidation. Last but not least, the electron transfer on carbon surface was enhanced by the incorporation of Co@C nanoparticles, which greatly improved the catalytic performance on EB oxidation. This study provides a new insight into the Co‐based catalysts in the aerobic oxidation of hydrocarbons.
Nickel(II)‐Catalyzed Selective(E)‐Olefination of Methyl Heteroarenes Using Benzyl Alcohols via Acceptorless Dehydrogenative Coupling Reaction
Authors: Balamurugan Gunasekaran , Ramesh Rengan
Published: November 2021

An efficient catalytic protocol for the synthesis of selective(E)‐olefins by the newly synthesized nickel complexes via greener acceptorless dehydrogenative coupling methodology is presented. Two nickel(II) N, S chelating complexes were structurally characterized with the aid of spectral and single crystal X‐ray diffraction methods. Olefination of 2‐methylheteroarenes with benzyl alcohols via acceptorless dehydrogenative coupling is achieved by inexpensive nickel(II) catalysts. The present olefination protocol is simple and furnishes the desired 2‐alkenylheteroarenes in 35 h and yields in the range of 40–93 %. The dehydrogenative coupling reaction proceeds via the generation of an aldehyde intermediate and produces water and hydrogen as sole by‐products. The wide substrate scope of this catalytic reaction covered the synthesis of drug intermediates.
Ring Size Determines the Conformation, Global Aromaticity and Photophysical Properties of Macrocyclic Oligofurans
Authors: Dishi Or , Malakar Partha , Shimon Linda J. W. , Ruhman Sanford , Gidron Ori
Published: November 2021

In π‐conjugated macrocycles, there is a trade‐off between the global and local expression of effects such as aromaticity, with the outcome of the trade‐off determined by the geometry and aromaticity of the constituent units. Compared with other aromatic rings, the aromatic character of furan is relatively small, and therefore global effects in macrocyclic furans are expected to be more pronounced. Following our introduction of macrocyclic oligofuran, we present the first synthesis of a series of π‐conjugated bifuran macrocycles of various ring sizes, from trimer to hexamer, and characterize them using both computational and experimental methods. The properties of macrocyclic oligofurans change considerably with size: The smaller trimer is rigid, weakly emissive and planar as revealed by its single crystal structure, and displays global antiaromaticity. In contrast, the larger pentamer and hexamer are flexible, emissive, have non‐planar structures, and exhibit local aromaticity. The results are supported by NICS and ACID calculations that indicate the global antiaromaticity of planar furan macrocycles, and by transient absorption measurements showing sharp absorption band for the trimer and only the internal conversion decay pathway.
Les rapports de responsabilité sociétale: Une étude des pratiques Canadiennes
Authors: Coulmont Michel , Berthelot Sylvie , Martineau Félix
Published: November 2021

The aim of this study is to identify the performance indicators that Canadian corporations voluntarily disclose based on the Global Reporting Initiative (GRI) and to examine their comparability. The results tend to show that all the companies studied disclose few indicators and that the format of these indicators makes comparisons impossible. Additional analyses revealed that while a minority of companies publish some indicators, the vast majority (91%) disclose poor quality information. Accordingly, the companies' strategy appears to be to muddy the waters than actually account for their performance.
Regioselective β‐Trifluoromethylation of β‐Silylporphyrins by Using a Trifluoromethyl Copper Complex
Authors: Hayashi Satoshi , Okamoto Akari , Nabekura Ryoto , Noji Masahiro , Takanami Toshikatsu
Published: November 2021

We developed a method for the regioselective β‐trifluoromethylation of β‐silylated Zn(II) porphyrins by using a phenanthroline and triphenylphosphine‐ligated trifluoromethyl–copper complex [(phen)(Ph3P)CuCF3]. The regioselective porphyrin trifluoromethylation, which occurs under mild conditions, exhibits excellent substrate generality and functional group compatibility.
N‐Thiocyanato‐2,10‐camphorsultam Derivatives: Design and Applications of Original Electrophilic Thiocyanating Reagents
Authors: Gao Mélissa , Vuagnat Martin , Jubault Philippe , Besset Tatiana
Published: November 2021

The synthesis of bench‐stable electrophilic thiocyanating reagents was depicted in two steps from readily available starting materials in good yields. These newly designed electrophilic reagents were successfully applied for the thiocyanation of different nucleophiles under mild and transition metal‐free conditions. Preliminary experiments for the asymmetric C3‐thiocyanation of an oxindole derivative were also conducted leading to the expected product with no induction of chirality, although opening possibilities for accessing chiral compounds.
Sustainable Lithium‐Ion Battery Separators Based on Poly(3‐Hydroxybutyrate‐Co‐Hydroxyvalerate) Pristine and Composite Electrospun Membranes
Authors: Barbosa João C. , Correia Daniela M. , Fidalgo-Marijuan Arkaitz , Gonçalves Renato , Fernandes Mariana , de Zea Bermudez Verónica , Silva Maria M. , Lanceros-Mendez Senentxu , Costa Carlos M.
Published: November 2021

To address the environmental issues related to lithium‐ion batteries, environmentally friendlier separators based on poly(hydroxybutyrate‐co‐hydroxyvalerate) (PHBV) membranes are prepared by electrospinning. Cobalt ferrite (CFO) fillers can be incorporated to improve the electrochemical properties of the membranes and it is shown that fiber orientation and CFO filler addition have no relevant effect on the physicochemical properties of membranes. PHBV membranes show a well‐defined porosity, resulting in liquid electrolyte retention above 300% by weight and an ionic conductivity at room temperature well above 1 mS cm−1, that depends on fiber orientation and filler addition. Battery separator performance is evaluated on half‐cells demonstrating a discharge capacity value of about 130 mAh g−1 at C/5‐rate with a relatively stable cycling behavior, independently of the electrospun membrane type. Composite membranes with oriented fibers show the best cycling behavior with 90 mAh g−1 at C/2‐rate. The results confirm that the addition of CFO improves the battery performance of the PHBV membranes. The composite membranes based on natural polymers, still poorly explored alternatives to synthetic polymers for battery applications, show good cycling performance are demonstrated. The studied composite membranes are attractive candidates for the next generation of environmentally friendlier natural polymer‐based separator membranes for lithium‐ion battery applications.
Specific age‐correlated activation of top hierarchical motor control areas during gait‐like plantar stimulation: An fMRI study
Authors: Jeanvoine Henry , Labriffe Matthieu , Tannou Thomas , Navasiolava Nastassia , Ter Minassian Aram , Girot Jean‐Baptiste , Leiber Louis‐Marie , Custaud Marc‐Antoine , Annweiler Cédric , Dinomais Mickaël
Published: November 2021

A better understanding of gait disorders that are associated with aging is crucial to prevent adverse outcomes. The functional study of gait remains a thorny issue due to technical constraints inherent to neuroimaging procedures, as most of them require to stay supine and motionless. Using an MRI‐compatible system of boots reproducing gait‐like plantar stimulation, we investigated the correlation between age and brain fMRI activation during simulated gait in healthy adults. Sixty‐seven right‐handed healthy volunteers aged between 20 and 77 years old (49.2 ± 18.0 years; 35 women) were recruited. Two paradigms were assessed consecutively: (a) gait‐like plantar stimulation and (b) chaotic and not gait‐related plantar stimulation. Resulting statistical parametric maps were analyzed with a multiple‐factor regression that included age and a threshold determined by Monte‐Carlo simulation to fulfill a family‐wise error rate correction of p < .05. In the first paradigm, there was an age‐correlated activation of the right pallidum, thalamus and putamen. The second paradigm showed an age‐correlated deactivation of both primary visual areas (V1). The subtraction between results of the first and second paradigms showed age‐correlated activation of the right presupplementary motor area (Brodmann Area [BA] 6) and right mid‐dorsolateral prefrontal cortex (BA9‐10). Our results show age‐correlated activity in areas that have been associated with the control of gait, highlighting the relevance of this simulation model for functional gait study. The specific progressive activation of top hierarchical control areas in simulated gait and advancing age corroborate a progressive loss of automation in healthy older adults.
Inflammatory bowel diseases in Tamil Nadu: A survey of demographics, clinical profile, and practices
Authors: Yewale Rohan V , Natarajan Kartik , Ubal Dhus Jeyaraj , Parameswaran Sarojini Ashok , Ramaswamy Palaniswamy Kallipatti , Babu Vinish Doraisamy , Somasundaram Aravindh , Ramakrishnan Arulraj , Karmegam Sibithooran , Arun Ramaswamy Saraswathy , Manmohan Ujjani Shankaraiah , Mahadevan Balakrishnan , Harri Prasad Baskkaran , Chandrasekar Toguluva Seshadri , Gokul Bollu Janakan , Dutta Amit , Joseph Anjilivelil Joseph , Venkatraman Jayanthi , Ganesh Panchapakesan , Shanmuganathan Subramanyam , Alagammai Palaniappan L , Ramasubramanian Ramalingam , Venkatakrishnan Leelakrishnan , Ganesan Ramamoorthi , Chandrasekaran Arun Arunachalam , Srinivas Sankaranarayanan , Kannan Mariappan , Revathy M Shanmugam , Sathiyasekaran Malathi , Sarangapani Arulprakash , Rajesh Natrajan , Arulselvan Velusamy , Aravind Arumugam , Premkumar Karunakaran , Kavitha Sampath , Varadarajulu Hema Vijayalakshmi , Manimaran Murugesan , Basumani Pandurangan , Murali Ananthavadivelu , Ramakrishna Balakrishnan Siddartha
Published: November 2021

Background

Inflammatory bowel disease (IBD) is increasingly diagnosed in South Asia. This survey by the Tamil Nadu Chapter of the Indian Society of Gastroenterology (TNISG) documents the demography, clinical profile, and therapeutic practices related to IBD in Tamil Nadu.

Methods

TNISG members from 32 institutions completed an online cross‐sectional questionnaire on IBD patients from March 2020 to January 2021.

Results

Of 1295 adult IBD patients, 654 had Crohn's disease (CD), 499 ulcerative colitis (UC), and 42 IBD‐unclassified (IBD‐U). CD and UC showed a unimodal age distribution. A total of 55% were graduates or postgraduates. A positive family history was noted in 30, other risk factors were uncommon. In CD, the pattern of involvement was ileocolonic (42.8%), ileal (34.7%), colonic (18.9%), and upper gastrointestinal (3.5%); while in UC, disease was characterized as extensive (44.9%), left‐sided (41.7%), or proctitis (13.4%). Perineal disease, perianal fistulae, and bowel obstruction were noted in 4.3, 14.0, and 23.5%, respectively, of CD. The most widely used drugs were mesalamine, azathioprine, and corticosteroids. Surgery was undertaken in 141 patients with CD and 23 patients with UC. Of the 138 patients with pediatric IBD (≤16 years), 23 were characterized as very early onset IBD (VEO‐IBD), 27 as early‐onset, and 88 as adolescent IBD. VEO‐IBD were more likely to have a positive family history of IBD and were more likely to have perineal disease and to have the IBD‐U phenotype. Among pediatric IBD patients, corticosteroids, mesalamine, and azathioprine were the most commonly used medications, while 25 pediatric patients received biologics.

Conclusion

This study provides important information on demography, clinical profile, and treatment practices of IBD in India.
HCV infection in hemophilia A patients is associated with altered cytokines and chemokines profile and might modulate the levels of FVIII inhibitor
Authors: Bolina‐Santos Eduarda , Chaves Daniel G. , da Silva‐Malta Maria C. F. , Carmo Ricardo A. , Barbosa‐Stancioli Edel F. , Lobato Martins Marina
Published: November 2021

Prevalence of hepatitis C virus (HCV) is high in hemophilia A patients and the development of FVIII inhibitor is another challenge in the management of these individuals. The influence of HCV infection in the occurrence of inhibitors was investigated by the comparison of clinical and laboratory data from noninfected (NI, n = 96) and chronically HCV‐infected (HCV, n = 58) hemophilia A patients. Concentrations of plasmatic cytokines (IL‐2, IL‐4, IL‐6, IL‐10, TNF, IFN‐γ, and IL‐17A) and chemokines (CCL2, CCL5, CXCL8, CXCL9, and CXCL10) were quantified from patients' samples. The results showed that older age, use of cryoprecipitate and fresh frozen plasma, and severe hemophilia were associated with HCV infection, whereas exclusive use of virus inactivated clotting factors was a protector factor to acquiring HCV infection. HCV infection was strongly associated with low levels of inhibitor (OR = 20.53, p < 0.001). Patients with a history of inhibitor (INB+) presented a mixed immune profile characterized by higher levels of pro‐and anti‐inflammatory cytokines than those without a history of inhibitor (INB−). The highest levels of CCL2 and CXCL8 were seen in HCVINB−, whereas CXCL9 and CXCL10 in HCVINB+. Heatmap analysis of the set of cytokines and chemokines concentration distributed HCV patients into two distinct clusters, HCVINB+ and HCVINB‐, both characterized by low concentrations of IL‐4, while noninfected patients were grouped in a single block regardless of inhibitor development history (NIINB−/INB+). This finding suggests that the strong association between HCV infection and low levels of factor VIII inhibitors might be due to the modulation of the cytokine and chemokine network established by the antiviral response.
Astragalus polysaccharide regulates brown adipocytes differentiation by miR‐6911 targeting Prdm16
Authors: Zhang Shihe , Song Pengkang , Chen Xiaoyou , Wang Yu , Gao Xuyang , Liang Lin , Zhao Junxing
Published: November 2021

Brown adipose tissue (BAT) is a specialized tissue in mammals related to thermogenesis. The Astragalus polysaccharide (APS) is the major natural active component of Astragalus membranaceus, which has been recognized as one of the most popular herbal medicines worldwide. The role and possible mechanisms of APS on brown adipocytes differentiation is not well defined. Here, we explored the effect of APS on the differentiation of brown adipocytes in C3H10T 1/2 cells. The results showed that APS promoted the differentiation of brown adipocytes and improved insulin sensitivity along with significant increases in the expression of brown adipogenic marker proteins (C/EBPα, C/EBPβ, and PPARγ), thermogenesis marker proteins (UCP1, PRDM16, and PGC‐1α), and insulin sensitivity marker protein (GLUT4). Meanwhile, the results showed that the amount of the phosphorylation of insulin receptor substrate 1 (p‐IRS1) and phospho‐AKT (p‐AKT) which are critical factors in the insulin signaling pathway was increased without changing the total amount of IRS and AKT. Furthermore, the results of RNA‐seq showed that APS altered the expression profiles of various miRNAs, and among which the expression of miR‐6911 as a universal regulatory factor was significantly decreased. Importantly, we found that miR‐6911 regulated the differentiation of brown adipocytes by targeting PR domain‐containing 16 (Prdm16). In addition, after transfection of miR‐6911 mimics, compared with the control and inhibitor group, PRDM16 protein expression significantly decreased, which was accompanied by the decrease of PPARγ, UCP1, and PGC‐1α. Collectively, our results indicated that APS regulated brown adipocytes differentiation in C3H10T 1/2 cells via miRNA‐6911 targeting Prdm16.
Carrier Injection and Annealing‐Enhanced Electrical Performance in Tunnel Oxide‐Passivated Contact Silicon Solar Cells
Authors: Hu Zechen , Song Lihui , Lin Dehang , He Qiyuan , Zhang Xiujuan , Cai Yongmei , Fang Lingxin , He Sheng , Hsu WeiChih , Yu Xuegong , Yang Deren
Published: November 2021

Herein, it is demonstrated that low temperature current injection and annealing (CIA) treatment can cause evident improvements in open circuit voltage, short‐circuit current, and fill factor of tunnel oxide‐passivated contact (TOPCon) silicon solar cells, leading to a notable conversion efficiency gain (over 0.4% absolute at the best condition). The effects of injected current and annealing temperatures toward the improvement of electrical performance of the TOPCon solar cells are compared. The more evident increase in the electrical performance after the CIA treatment may come from the higher fill factor improvements, which can be induced by the change of contact resistance after the CIA treatment, the potential involvement of hydrogen is discussed. The CIA treatment can be a reliable approach to further enhance the conversion efficiency of TOPCon solar cells, which is of great significance for the global PV industry.
Topographic Cues Guiding Cell Polarization via Distinct Cellular Mechanosensing Pathways
Authors: Liu Wei , Sun Qian , Zheng Zi‐Li , Gao Ya‐Ting , Zhu Guan‐Yin , Wei Qiang , Xu Jia‐Zhuang , Li Zhong‐Ming , Zhao Chang‐Sheng
Published: November 2021

Cell polarization exists in a variety of tissues to regulate cell behaviors and functions. Space constraint (spatially limiting cell extension) and adhesion induction (guiding adhesome growth) are two main ways to induce cell polarization according to the microenvironment topographies. However, the mechanism of cell polarization induced by these two ways and the downstream effects on cell functions are yet to be understood. Here, space constraint and adhesion induction guiding cell polarization are achieved by substrate groove arrays in micro and nano size, respectively. Although the morphology of polarized cells is similar on both structures, the signaling pathways to induce the cell polarization and the downstream functions are distinctly different. The adhesion induction (nano‐groove) leads to the formation of focal adhesions and activates the RhoA/ROCK pathway to enhance the myosin‐based intracellular force, while the space constraint (micro‐groove) only activates the formation of pseudopodia. The enhanced intracellular force caused by adhesion induction inhibits the chromatin condensation, which promotes the osteogenic differentiation of stem cells. This study presents an overview of cell polarization and mechanosensing at biointerface to aid in the design of novel biomaterials.
Precisely Defining Local Gradients of Stimuli‐Responsive Hydrogels for Complex 2D‐to‐4D Shape Evolutions
Authors: Yin Jincai , Fan Wenxin , Xu Zihan , Duan Jinghua , Xia Yanzhi , Nie Zhihong , Sui Kunyan
Published: November 2021

The intellectualization and complication of existing self‐shaping materials are limited by the inseparable monotonic relationship between their deformation rate and deformation degree (i.e., a higher deformation rate is accompanied by a high deformation degree). This causes that they can only deform from 2D to 3D states. Here, a simple yet versatile strategy to decouple the monotonic correlation between the deformation rate and deformation degree of self‐shaping hydrogels is presented for achieving complex deformations from 2D to temporary 3D to 3D (2D‐to‐4D). It is demonstrated that when the gradient hydrogels prepared by photopolymerization possess dense polymer networks, the local regions with a high deformation rate can exhibit a low deformation degree. The resulting hydrogels can thus deform in a novel 2D‐to‐4D mode under external stimuli. During the deformation, they first transform into the temporary shapes induced by the local deformation rate difference, and then transform into the final shapes determined by the local deformation degree difference. Through controlling the ultraviolet irradiation direction and time to precisely program the local gradients of self‐shaping hydrogels, they can be designed to produce various unprecedented yet controllable 2D‐to‐4D shape evolutions on demand, such as transformable origami, sequential gesture actions in finger‐guessing games, mobile octopuses, time switch, etc.
Low‐Cost Strategy for High‐Efficiency Bifacial Perovskite/c‐Si Tandem Solar Cells
Authors: Du Daxue , Gao Chao , Zhang Dezhao , Qiao Feiyang , Liang Jingjing , Wang Haiyan , Shen Wenzhong
Published: November 2021

Many studies have confirmed that the perovskite/crystalline silicon (c‐Si) tandem solar cells (TSCs) can achieve excellent photovoltaic performance far exceeding that of single‐junction solar cells. However, the quite thick c‐Si bottom‐cells have to be used to fully absorb near‐infrared photons, which greatly improves the cost of the TSCs. The bifacial two‐terminal TSCs not only can improve the energy output by introducing rear incident light, but also significantly reduce the Si thickness while maintaining high efficiency. Herein, the photovoltaic performance of bifacial perovskite/c‐Si TSCs under different Si thicknesses, pyramid heights, and albedos have been calculated. It is found that the thickness of the c‐Si sub‐cells can be reduced from the current 250 to 25 μm, and only the albedos need to be increased by 18.6% to cover the absorption loss in the near‐infrared. It is recommended that 100‐μm thick c‐Si is a suitable candidate and optimized the size of the Si pyramids (1.0 μm) to obtain excellent light trapping performance. This work can serve as a guidance for experimental preparation of low‐cost and high‐efficiency bifacial perovskite/c‐Si TSCs.
Effect of Top‐Swirling Turbulence Inhibitor on Multiphase Flow in a Single‐Strand Tundish During Transient Casting
Authors: Zhang Hua , Wang Jiahui , Fang Qing , Wu Guoliang , Zhao Peng , Ni Hongwei
Published: November 2021

The turbulence and multiphase flows in a single‐strand slab casting tundish during the start‐up operation, steady‐state casting, and the ladle changeover process without a turbulence inhibitor (TI), with an ordinary TI, and with a top‐swirling TI are numerically investigated and compared to assess the metallurgical advantages of a top‐swirling TI. The results show that the designed top‐swirling TI has no negative effect on the turbulence flow of molten steel during steady‐state casting, as the swirling flow may enhance the inclusion removal rate, and erosion of the guide vanes is relatively weak. During start‐up operation, the use of a top‐swirling TI effectively alleviated level fluctuations in the impact zone, which decreased from 38.75 mm at 90 s to 12.5 mm at the start‐up tonnage, then decreased to zero within 180 s. During ladle changeover, the second stage of steel exposure could be eliminated by the top‐swirling TI, while the areas of steel exposure remaine around 1550 and 750 cm2 without a TI and with an ordinary TI after 60 s of refilling time. The top‐swirling TI could effectively improve the turbulence flow of molten steel, avoiding secondary oxidation and slag entrapment, making it suitable for widespread application and popularization.
Emissions- und staufreier alpenquerender Güterverkehr: Wachstumspotenziale und -hürden für den Verkehrsträger Schiene am Beispiel „Brenner-Pass“
Authors: Weidemann Hans-Jürgen
Published: November 2021

Die Staaten Europas laufen Gefahr, ihre ambitionierten verkehrs- und klimapolitischen Ziele für den Güterverkehr zu verfehlen. Zugleich sind wesentliche Kernstrecken in Europa durch den massiven Lkw-Verkehr überlastet. Dem nur langsamen Ausbau der Fernstraßen steht eine signifikante Zunahme der Transportleistung durch schwere Lkw gegenüber. Europas Straßenverkehr drohen Fahrermangel, Dauerstau und Kostensteigerung. Bereits seit 2010 übersteigt die Transportleistung im Straßengüterverkehr mit über 400 Mrd. Tonnen- Kilometer die Kapazität der Autobahnen. Grafik 1 zeigt die tatsächliche Verkehrsleistung in Mrd. Tonnenkilometern (rote Kurve), welche die nominale Kapazität der Bundesautobahnen in Deutschland seit etwa 2010 übersteigt (schwarze Kurve) – und die Anzahl der Staus in Deutschland, die sich seit der Überlastung der Autobahnen in nur sechs Jahren vervierfacht hat.
Herausforderungen im internationalen Schienenfernverkehr in Europa
Authors: Kampp Marco
Published: November 2021

Ein wichtiger Bestandteil der grenzüberschreitenden Mobilität in Europa ist der internationalen Schienenfernverkehr. Dieser Beitrag gibt einen kurzen Überblick über die Entwicklung des internationalen Schienenfernverkehrs und möchte auf bestehende Herausforderungen in einem europäischen Kontext hinweisen.
Europäische Verkehrspolitik
Authors: Dorfmann Herbert
Published: November 2021

Bereits im Vertrag von Rom, unterzeichnet im Jahre 1957, hoben die Mitgliedstaaten der Europäischen Wirtschaftsgemeinschaft die Bedeutung einer gemeinsamen Verkehrspolitik (Art 74–Art 84) die neben der Agrar- und Handelspolitik zu den ersten gemeinsamen Politikbereichen der Gemeinschaft gehörte, hervor. Die Einführung einer gemeinsamen Verkehrspolitik erfolgte jedoch erst nach einer Untätigkeitsklage des Europäischen Parlaments und dem Urteil des Europäischen Gerichtshofs vom 22. Mai 1985. Der Rat wurde darin aufgefordert tätig zu werden und die Entwicklung einer gemeinsamen Verkehrspolitik in die Wege zu leiten.
Praktische Herausforderungen und Zukunftsvisionen im internationalen Personen- und Güterverkehr – Eine Podiumsdiskussion
Authors: Huber Eva Maria
Published: November 2021

Am 1. Februar 2019 fand an der Universität Innsbruck eine moderierte Podiumsdiskussion statt, im Rahmen derer Expertinnen und Experten aus der Transportwirtschaft zum gedanklichen Austausch über den Personen- und Güterverkehr in Europa zusammenkamen. Die Veranstaltung diente nicht nur der Bestandsaufnahme, auch Zukunftsvisionen für den Personen- und Güterverkehr wurden ausgiebig diskutiert. Dazu zeigten die Teilnehmenden auf, in welchen Bereichen aus praktischer Sicht derzeit akuter Regelungsbedarf besteht. Daneben sorgte auch die Mobilität in der Europaregion Tirol-Südtirol-Trentino bei allen Teilnehmenden für Diskussionsstoff. Insgesamt konnten viele wertvolle Erkenntnisse gesammelt werden, die hier dokumentiert und im Anschluss aus rechtswissenschaftlicher Sicht bewertet werden sollen. Zunächst werden die einzelnen Diskussionsbeiträge kurz dargestellt.
Il trasporto multimodale nel diritto dell’Unione Europea: un fenomeno trasportistico emergente privo di un’adeguata regolamentazione
Authors: Perathoner Christoph
Published: November 2021

A settant’anni dalla lungimirante dichiarazione dell’allora Ministro degli Esteri francese Robert Schuman (1886–1963) il 9 maggio 1950 a Parigi, è possibile constatare come il lungo e sempre fragile processo di integrazione europea, finalizzato a realizzare “un’unione sempre più stretta tra i popoli dell’Europa”, abbia permesso il raggiungimento di obiettivi che hanno fondamentalmente migliorato la convivenza e la cooperazione sul nostro continente. In tal senso, un traguardo essenziale per gli Stati membri dell’UE è rappresentato dalla creazione di un mercato interno che assicura “la libera circolazione delle merci, delle persone, dei servizi e dei capitali”. Invero, l’istaurazione del mercato interno – al pari dell’integrazione europea – è un processo in continua evoluzione. La ratio istitutiva di un mercato unico sul continente europeo è quella di creare i presupposti per una crescita economica equilibrata, per ottenere la stabilità dei prezzi, per poter costruire un’economia sociale di mercato fortemente competitiva, che miri alla piena occupazione e al progresso sociale, e tutto questo con l’impegno di raggiungere un elevato livello di tutela e di miglioramento della qualità dell’ambiente e della vita delle persone.
Die Querbezüge zwischen UN-Kaufrecht (CISG) und COTIF-Eisenbahngüterbeförderungsrecht (CIM)
Authors: Koller Thomas
Published: November 2021

Ein beachtlicher Teil des grenzüberschreitenden Warenhandels erfolgt per Eisenbahntransport. Zwischen dem internationalen Kaufrecht und dem Eisenbahngüterbeförderungsrecht bestehen daher zahlreiche Berührungspunkte. Viele dieser Gütertransaktionen unterliegen kaufrechtlich dem CISG und transportrechtlich den Einheitlichen Rechtsvorschriften für den Vertrag über die internationale Eisenbahnbeförderung von Gütern (CIM). Der folgende Beitrag analysiert verschiedene Probleme an den Schnittstellen zwischen dem UN-Kaufrecht und den CIM.
La smart mobility nell’ordinamento giuridico dell’UE e le potenzialità di sviluppo nelle città europee
Authors: Perathoner Christoph
Published: November 2021

L’emergenza epidemiologica da COVID-19, che, partendo dalla Cina, in poche settimane si è propagata in tutti i continenti di questo pianeta, mettendone in ginocchio la popolazione, ha legittimato i governi di molti Paesi ad emanare provvedimenti restrittivi, conferendo di fatto agli Stati il potere di comprimere le libertà e i diritti fondamentali dei singoli in maniera del tutto inedita per le nostre generazioni.
Wartezeiten auf einen Psychotherapieplatz vor und nach der Psychotherapiestrukturreform
Authors: Singer Susanne , Maier Lena , Paserat Anke , Lang Klaus , Wirp Bernhild , Kobes Jörg , Porsch Udo , Mittag Martina , Toenges Gerrit , Engesser Deborah
Published: November 2021

Hintergrund und Fragestellung

Die Psychotherapiestrukturreform im Jahr 2017 verfolgte u. a. das Ziel, die Wartezeiten auf Psychotherapien zu verringern. Diese Studie ging der Frage nach, ob dieses Ziel erreicht wurde.

Methoden

Psychotherapiepraxen aus 7 Bundesländern entnahmen ihren Akten die Daten für Erstkontakt, Erstgespräch und Behandlungsbeginn. Der Vergleich der Wartezeiten auf ein Erstgespräch und auf den Beginn der Behandlung vor vs. nach der Reform erfolgte mithilfe von Kaplan-Meier-Kurven und stratifizierten Log-Rank-Tests.

Ergebnis

Akten von 1548 Patienten aus 9 Praxen wurden ausgewertet. Die durchschnittliche Wartezeit auf ein Erstgespräch lag sowohl vor als auch nach der Reform bei 3 Wochen (p = 0,20). Die Zeit zwischen der Anmeldung und dem Behandlungsbeginn erhöhte sich von durchschnittlich 18 auf 20 Wochen, wobei nach der Reform v. a. die sehr kurzen Wartezeiten (<10 Wochen) abnahmen (p = 0,0004).

Diskussion

Die in den Praxen dokumentierten Daten liefern keine Anhaltspunkte dafür, dass sich die Wartezeit auf Erstgespräche bei Psychotherapeuten verkürzt hat. Das Warten auf einen Psychotherapieplatz scheint insgesamt etwas länger geworden zu sein, sodass in dieser Hinsicht keine Verbesserung der Versorgung durch die Reform festgestellt werden konnte.
Integrated exposure–response analysis of efficacy and safety of lurbinectedin to support the dose regimen in small-cell lung cancer
Authors: Fernández-Teruel Carlos , Fudio Salvador , Lubomirov Rubin
Published: November 2021

Purpose

These exposure–response (E–R) analyses integrated lurbinectedin effects on key efficacy and safety variables in relapsed SCLC to determine the adequacy of the dose regimen of 3.2 mg/m2 1-h intravenous infusion every 3 weeks (q3wk).

Methods

Logistic models and Cox regression analyses were applied to correlate lurbinectedin exposure metrics (AUCtot and AUCu) with efficacy and safety endpoints: objective response rate (ORR) and overall survival (OS) in SCLC patients (n = 99) treated in study B-005 with 3.2 mg/m2 q3wk, and incidence of grade 4 (G4) neutropenia and grade 3–4 (G ≥ 3) thrombocytopenia in a pool of cancer patients from single-agent phase I to III studies (n = 692) treated at a wide range of doses. A clinical utility index was used to assess the appropriateness of the selected dose.

Results

Effect of lurbinectedin AUCu on ORR best fitted to a sigmoid-maximal response (Emax) logistic model, where Emax was dependent on chemotherapy-free interval (CTFI). Cox regression analysis with OS found relationships with both CTFI and AUCu. An Emax logistic model for G4 neutropenia and a linear logistic model for G ≥ 3 thrombocytopenia, which retained platelets and albumin at baseline and body surface area, best fitted to AUCtot and AUCu. AUCu between approximately 1000 and 1700 ng·h/L provided the best benefit/risk ratio, and the dose of 3.2 mg/m2 provided median AUCu of 1400 ng·h/L, thus maximizing the proportion of patients within that lurbinectedin target exposure range.

Conclusions

The relationships evidenced in this integrated E–R analysis support a favorable benefit-risk profile for lurbinectedin 3.2 mg/m2 q3wk.

Trial registration

Clinicaltrials.gov: NCT02454972; registered May 27, 2015.
An ALNS algorithm for the static dial-a-ride problem with ride and waiting time minimization
Authors: Pfeiffer Christian , Schulz Arne
Published: November 2021

The paper investigates the static dial-a-ride problem with ride and waiting time minimization. This is a new problem setting of significant practical relevance because several ride-sharing providers launched in recent years in large European cities. In contrast to the standard dial-a-ride problem, these providers focus on the general public. Therefore, they are amongst others in competition with taxis and private cars, which makes a more customer-oriented objective necessary. We present an adaptive large neighbourhood search (ALNS) as well as a dynamic programming algorithm (DP), which are tested in comprehensive computational studies. Although the DP can only be used for a single tour and, due to the computational effort, as a restricted version or for small instances, the ALNS also works efficiently for larger instances. The results indicate that ride-sharing proposals may help to solve the trade-off between individual transport, profitability of the provider, and reduction of traffic and pollution.
The Rat Genome Database (RGD) facilitates genomic and phenotypic data integration across multiple species for biomedical research
Authors: Kaldunski M. L. , Smith J. R. , Hayman G. T. , Brodie K. , De Pons J. L. , Demos W. M. , Gibson A. C. , Hill M. L. , Hoffman M. J. , Lamers L. , Laulederkind S. J. F. , Nalabolu H. S. , Thorat K. , Thota J. , Tutaj M. , Tutaj M. A. , Vedi M. , Wang S. J. , Zacher S. , Dwinell M. R. , Kwitek A. E.
Published: November 2021

Model organism research is essential for discovering the mechanisms of human diseases by defining biologically meaningful gene to disease relationships. The Rat Genome Database (RGD, (https://rgd.mcw.edu)) is a cross-species knowledgebase and the premier online resource for rat genetic and physiologic data. This rich resource is enhanced by the inclusion and integration of comparative data for human and mouse, as well as other human disease models including chinchilla, dog, bonobo, pig, 13-lined ground squirrel, green monkey, and naked mole-rat. Functional information has been added to records via the assignment of annotations based on sequence similarity to human, rat, and mouse genes. RGD has also imported well-supported cross-species data from external resources. To enable use of these data, RGD has developed a robust infrastructure of standardized ontologies, data formats, and disease- and species-centric portals, complemented with a suite of innovative tools for discovery and analysis. Using examples of single-gene and polygenic human diseases, we illustrate how data from multiple species can help to identify or confirm a gene as involved in a disease and to identify model organisms that can be studied to understand the pathophysiology of a gene or pathway. The ultimate aim of this report is to demonstrate the utility of RGD not only as the core resource for the rat research community but also as a source of bioinformatic tools to support a wider audience, empowering the search for appropriate models for human afflictions.
Hydrogen Sulfide Inhibits Cadmium-Induced Cell Death of Cucumber Seedling Root Tips by Protecting Mitochondrial Physiological Function
Authors: Luo Shilei , Tang Zhongqi , Yu Jihua , Liao Weibiao , Xie Jianming , Lv Jian , Liu Zeci , Calderón-Urrea Alejandro
Published: November 2021

Hydrogen sulfide (H2S) can alleviate Cd-induced cell death, but the molecular mechanisms are not clear. To shed light on these mechanisms, cell death induced by 200 μM cadmium chloride in cucumber seedlings root tips was used as a model system. Here, we report that the negative effect of Cd stress in mitochondrial physiological functions include changes in cytochrome c/a, mitochondrial membrane permeability transition pores, and adenosine triphosphatase (ATPase). Moreover, Cd stress led to the release of mitochondrial Ca2+into the cytosol. Exogenous application of sodium hydrosulfide (NaHS, a donor of H2S) inhibited cell death and maintains mitochondrial function by reducing mitochondrial hydrogen peroxide accumulation, increasing ATPase activity and down-regulatingCsVDACandCsANTexpression. In summary, H2S suppressed Cd-induced cell death by improving mitochondrial physiological properties.
Dorsal instrumentation with and without vertebral body replacement in patients with thoracolumbar osteoporotic fractures shows comparable outcome measures
Authors: Schwendner Maximilian , Motov Stefan , Ryang Yu-Mi , Meyer Bernhard , Krieg Sandro M.
Published: November 2021

Purpose

In the surgical treatment of osteoporotic spine fractures, there is no clear recommendation, which treatment is best for the individual patient with vertebra plana and/or neurological deficit requiring instrumentation. The aim of this study was to evaluate clinical and radiological outcomes after dorsal or 360° instrumentation of osteoporotic fractures of the thoracolumbar spine in a cohort of patients representing clinical reality.

Methods

A total of 116 consecutive patients were operated on between 2008 and 2020. Inclusion criteria were osteoporotic fracture, thoracolumbar location, and dorsal instrumentation. In 79 cases, vertebral body replacement (VBR) was performed additionally. Patient outcomes including complications, EQ-5D at follow-up, and sagittal correction were analyzed.

Results

Medical and surgical complications occurred in 59.5% of patients with 360° instrumentation compared to 64.9% of patients with dorsal instrumentation only (p = 0.684). Dorsal instrumentation plus VBR resulted in a sagittal correction of 9.3 ± 7.4° (0.1–31.6°) compared to 6.0 ± 5.6° (0.2–22.8°) after dorsal instrumentation only, respectively (p = 0.0065). EQ-5D was completed by 79 patients after 4.00 ± 2.88 years (0.1–11.8 years) and was 0.56 ± 0.32 (− 0.21–1.00) for VBR compared to 0.56 ± 0.34 (− 0.08–1.00) without VBR after dorsal instrumentation (p = 0.994).

Conclusion

360° instrumentation represents a legitimate surgical technique with no additional morbidity even for the elderly and multimorbid osteoporotic population. Particularly, if sufficient long-term construct stability is in doubt or ventral stenosis is present, there is no need to abstain from additional ventral reinforcement and decompression.
Tumefactive demyelinating CNS lesion in a 60-year-old woman with familial Mediterranean fever
Authors: Trostel Constanze , Laichinger Kornelia , Hauser Till-Karsten , Saur Sebastian , Krumbholz Markus , Henes Jörg , Ziemann Ulf , Kowarik Markus C.
Published: November 2021

We here report on a 60-year-old woman with familial Mediterranean fever (FMF) who developed cognitive impairment 16 years after initial diagnosis. On MRI, a new extensive white matter lesion in the right frontal lobe with mild local mass effect but without contrast enhancement was detectable and classified as a tumefactive lesion. Additional MR spectroscopy showed markedly increased choline levels accompanied by a significant lactate peak, highly suggestive of a low-florid demyelinating process. Although diffuse central nervous system (CNS) lesions have been described in single FMF cases, tumefactive lesions have not been observed in FMF patients without concomitant multiple sclerosis. In summary, this case highlights rare differential diagnoses of atypical, inflammatory CNS lesions and the clinical utility of MR spectroscopy.
Improving medical residents’ self-assessment of their diagnostic accuracy: does feedback help?
Authors: Kuhn Josepha , van den Berg Pieter , Mamede Silvia , Zwaan Laura , Bindels Patrick , van Gog Tamara
Published: November 2021

When physicians do not estimate their diagnostic accuracy correctly, i.e. show inaccurate diagnostic calibration, diagnostic errors or overtesting can occur. A previous study showed that physicians’ diagnostic calibration for easy cases improved, after they received feedback on their previous diagnoses. We investigated whether diagnostic calibration would also improve from this feedback when cases were more difficult. Sixty-nine general-practice residents were randomly assigned to one of two conditions. In the feedback condition, they diagnosed a case, rated their confidence in their diagnosis, their invested mental effort, and case complexity, and then were shown the correct diagnosis (feedback). This was repeated for 12 cases. Participants in the control condition did the same without receiving feedback. We analysed calibration in terms of (1) absolute accuracy (absolute difference between diagnostic accuracy and confidence), and (2) bias (confidence minus diagnostic calibration). There was no difference between the conditions in the measurements of calibration (absolute accuracy, p = .204; bias, p = .176). Post-hoc analyses showed that on correctly diagnosed cases (on which participants are either accurate or underconfident), calibration in the feedback condition was less accurate than in the control condition, p = .013. This study shows that feedback on diagnostic performance did not improve physicians’ calibration for more difficult cases. One explanation could be that participants were confronted with their mistakes and thereafter lowered their confidence ratings even if cases were diagnosed correctly. This shows how difficult it is to improve diagnostic calibration, which is important to prevent diagnostic errors or maltreatment.