bluuebunny/crossref_metadata_2025_split huggingface dataset:
Endo/Lysosome‐Escapable Delivery Depot for Improving BBB Transcytosis and Neuron Targeted Therapy of Alzheimer's Disease
Authors: Cai Lulu , Yang Chuanyao , Jia Wenfeng , Liu Yuwei , Xie Rou , Lei Ting , Yang Zhihang , He Xueqin , Tong Rongsheng , Gao Huile 
Published: May 2020

AbstractThe effective treatment of Alzheimer's disease (AD) is hindered due to the hard blood–brain barrier (BBB) penetration and non‐selective distribution of drugs in the brain. Moreover, the complicated pathological mechanism of AD involves various pathway dysfunctions that limit the effectiveness of a single therapeutic drug. Herein, a dendrigraft poly‐l‐lysines (DGL)‐based siRNA and D peptide (Dp) loaded nanoparticle is designed that could target and penetrate through the BBB, enter the brain parenchyma, and further accumulate at the AD lesion. In this system, T7 peptide, which specifically targets transferrin receptors on the BBB, is linked to DGL via acid‐cleavable long polyethylene glycol (PEG) to achieve high internalization, quick escape from endo/lysosome, and effective transcytosis. Then, the Tet1, which specifically targets diseased neurons, is modified onto DGL by short PEG. After being exposed, Tet1 could drive the nanoparticles to the AD lesion and release the drugs. As a result, the production of β amyloid plaques (Aβ) is inhibited. Neurotoxicity induced by Aβ plaques and tau proten phosphorylation (p‐tau) tangle is also alleviated, and the cognition of AD mice is significantly improved. Overall, this system programmatically targets BBB and neurons, thus, significantly enhances the intracephalic drug accumulation and AD treatment efficacy.
Laboratory studies on dissolution of nitrogen fertilizers by humidity and precipitation
Authors: Sigtryggsson Christian , Hamnér Karin , Kirchmann Holger 
Published: May 2020

AbstractAiming at improving fertilizer management by assessing fertilizer dissolution, we compared the hygroscopicity of calcium ammonium nitrate (CAN), ammonium nitrate (NS 27‐4), and nitrate compounds (laboratory grade). Dissolution of N fertilizers was also studied under simulated rain conditions. All compounds were highly hygroscopic, dissolving within 24 h at 90–99% relative humidity and 25 °C. Addition of 2 mm rain to fertilizer granules (3–4.5 mm diam.) was sufficient to dissolve 50% of the compounds. Dissolution rates by humidity or rain were not the limiting step for plant availability.
Recent Advances in Vanadium‐Based Aqueous Rechargeable Zinc‐Ion Batteries
Authors: Liu Shude , Kang Ling , Kim Jong Min , Chun Young Tea , Zhang Jian , Jun Seong Chan 
Published: May 2020

AbstractAqueous zinc‐ion batteries (AZIBs) have attracted considerable attention as promising next‐generation power sources because of the abundance, low cost, eco‐friendliness, and high security of Zn resources. Recently, vanadium‐based materials as cathodes in AZIBs have gained interest owing to their rich electrochemical interaction with Zn2+ and high theoretical capacity. However, existing AZIBs are still far from meeting commercial requirements. This article summarizes recent advances in the rational design of vanadium‐based materials toward AZIBs. In particular, it highlights various tactics that have been reported to increase the intercalation space, structural stability, and the diffusion ability of the guest Zn2+, as well as explores the structure‐dependent electrochemical performance and the corresponding energy storage mechanism. Furthermore, this article summarizes recent achievements in the optimization of aqueous electrolytes and Zn anodes to resolve the issues that remain with Zn anodes, including dendrite formation, passivation, corrosion, and the low coulombic efficiency of plating/stripping. The rationalization of these research findings can guide further investigations in the design of cathode/anode materials and electrolytes for next‐generation AZIBs.
Demand response scheduling under uncertainty: Chance‐constrained framework and application to an air separation unit
Authors: Kelley Morgan T. , Baldick Ross , Baldea Michael 
Published: May 2020

AbstractRecent increases in renewable power generation challenge the operation of the power grid: generation rates fluctuate in time and are not synchronized with power demand fluctuations. Demand response (DR) consists of adjusting user electricity demand to match available power supply. Chemical plants are appealing candidates for DR programs; they offer large, concentrated loads that can be modulated via production scheduling. Price‐based DR is a common means of engaging industrial entities; its benefits increase significantly when a longer (typically, a few days) scheduling time horizon is considered. DR production scheduling comes with its own challenges, related to uncertainty in future (i.e., forecast) electricity prices and product demand. In this work, we provide a framework for DR production scheduling under uncertainty based on a chance‐constrained formulation that also accounts for the dynamics of the production facility. The ideas are illustrated with an air separation unit case study.
Gonadal dysfunction and beyond: Clinical challenges in children, adolescents, and adults with 47,XXY Klinefelter syndrome
Authors: Zitzmann Michael , Rohayem Julia 
Published: May 2020

AbstractKlinefelter syndrome (KS) is the most frequent sex chromosomal aneuploidy. The karyotype 47,XXY originates from either paternal or maternal meiotic nondisjunction during gametogenesis. KS males are very likely to exhibit marked gonadal dysfunctions, presenting both in severely attenuated spermatogenesis as well as hypergonadotropic hypogonadism. In addition, neurocognitive and psychosocial impairments, as well as cardiovascular, metabolic and bone disorders are often found in KS and might explain for an increased morbidity/mortality. All conditions in KS are likely to be induced by both gene overdosage effects resulting from supernumerary X‐chromosomal genes as well as testosterone deficiency. Notwithstanding, the clinical features are highly variable between KS men. Symptoms can become obvious at infancy, childhood, or adolescence. However, the majority of KS subjects is diagnosed during adulthood. KS adolescents require specific attention regarding pubertal development, in order to exploit their remaining fertility potential and allow for timely and tailored testosterone replacement. The chances for sperm retrieval might decline with age and could be hampered by testosterone replacement; therefore, cryostorage of spermatozoa is an option during adolescence, before the decompensation of endocrine and exocrine testicular functions becomes more overt. Sperm from semen or surgically retrieved, in combination with intracytoplasmic sperm injection enables KS males to become biological fathers of healthy children. The aim of this article is to present the current knowledge on KS, to guide clinical care and to highlight research needs.
Neuropsychological functions, sleep, and mental health in adults with Klinefelter syndrome
Authors: Fjermestad Krister W. , Huster Rene , Thunberg Christina , Stokke Simen , Gravholt Claus H. , Solbakk Anne‐Kristin 
Published: May 2020

AbstractA few studies have examined neuropsychological functions, sleep, and mental health combined in Klinefelter syndrome (KS; 47,XXY). We investigated neuropsychological functions with standard tests, sleep with actigraphy, and self‐reported mental health in 30 men with KS (Mean age = 36.7 years) compared to 21 controls (Mean age = 36.8 years). Men with KS scored significantly lower on mental speed, attention span, working memory, inhibition, and set‐shifting tests, as well as overall IQ (mean effect size difference Cohen's d = 0.79). Men with KS had significantly longer night wakes, with no differences in other sleep variables (mean d = 0.34). Men with KS reported poorer mental health than controls (mean d = 1.16). Regression analyses showed neuropsychological functions explained variance in some sleep domains for men with KS but not for controls. Neuropsychological functions explained variance in some mental health domains for controls. For men with KS, however, verbal IQ was the only significant predictor of mental health. Altogether, men with KS display problems in neuropsychological functions and mental health but do not appear different from controls on most sleep parameters. Our findings indicate that relations between neuropsychological functions, sleep, and mental health differ between men with KS and controls.
Kalium‐Polyheptazinimid: Ein übergangsmetallfreier Festkörper‐Triplett‐Sensibilisator in Kaskadenenergietransfer und [3+2]‐Cycloadditionen
Authors: Savateev Aleksandr , Tarakina Nadezda V. , Strauss Volker , Hussain Tanveer , ten Brummelhuis Katharina , Sánchez Vadillo José Manuel , Markushyna Yevheniia , Mazzanti Stefano , Tyutyunnik Alexander P. , Walczak Ralf , Oschatz Martin , Guldi Dirk M. , Karton Amir , Antonietti Markus 
Published: May 2020

AbstractPolymere Kohlenstoffnitridmaterialien wurden erfolgreich in zahlreichen Anwendungen zur Umwandlung von Licht in Energie, die von der Photokatalyse bis zur Optoelektronik reichen, eingesetzt. Für eine neue Anwendung und Modellierung verfeinerten wir zunächst die Kristallstruktur von Kalium‐Polyheptazinimid (K‐PHI) – einem Referenz‐Kohlenstoffnitridmaterial in der Photokatalyse – mithilfe von Röntgenpulverdiffraktometrie und Transmissionselektronenmikroskopie. Unter Verwendung der Kristallstruktur von K‐PHI wurden periodische DFT‐Berechnungen durchgeführt, um die Zustandsdichte zu berechnen und Intra‐Banden‐Zustände (IBS) zu lokalisieren. Es wurde festgestellt, dass IBS für die erhöhte Absorption von K‐PHI im nahen IR‐Bereich verantwortlich sind, als Elektronenfallen dienen und bei Energietransferreaktionen nützlich sind. Einmal mit sichtbarem Licht angeregt, können Kohlenstoffnitride neben der direkten Rekombination auch Intersystem Crossing vom Singulett‐ in den Triplett‐Zustand durchlaufen. Wir nutzen die angeregten zentrierten Triplett‐Zustände im K‐PHI, um eine Kaskade von Energieübertragungsreaktionen auszulösen und im Gegenzug z. B. Singulett‐Sauerstoff (1O2), als Ausgangspunkt für die Synthese von bis zu 25 verschiedenen N‐reichen Heterozyklen, zu sensibilisieren.
TiCl3‐Mediated Synthesis of 2,3,3‐Trisubstituted Indolenines: Total Synthesis of (+)‐1,2‐Dehydroaspidospermidine, (+)‐Condyfoline, and (−)‐Tubifoline
Authors: Delayre Bastien , Piemontesi Cyril , Wang Qian , Zhu Jieping 
Published: May 2020

Abstract2,3,3‐Trisubstituted indolenine constitutes an integral part of many biologically important monoterpene indole alkaloids. We report herein an unprecedented access to this skeleton by a TiCl3‐mediated reductive cyclization of tetrasubstituted alkenes bearing a 2‐nitrophenyl substituent. The proof of concept is demonstrated firstly by accomplishing a concise total synthesis of (+)‐1,2‐dehydroaspidospermidine featuring a late‐stage application of this key transformation. A sequence of reduction of nitroarene to nitrosoarene followed by 6π‐electron‐5‐atom electrocyclization and a 1,2‐alkyl shift of the resulting nitrone intermediate was proposed to account for the reaction outcome. A subsequent total synthesis of (+)‐condyfoline not only illustrates the generality of the reaction, but also provides a mechanistic insight into the nature of the 1,2‐alkyl shift. The exclusive formation of (+)‐condyfoline indicates that the 1,2‐alkyl migration follows a concerted Wagner–Meerwein pathway, rather than a stepwise retro‐Mannich/Mannich reaction sequence. Conditions for almost quantitative conversion of (+)‐condyfoline to (−)‐tubifoline by way of a retro‐Mannich/1,3‐prototropy/transannular cyclization cascade are also documented.
Lead‐Free Halide Double Perovskite Cs2AgBiBr6 with Decreased Band Gap
Authors: Ji Fuxiang , Klarbring Johan , Wang Feng , Ning Weihua , Wang Linqin , Yin Chunyang , Figueroa José Silvestre Mendoza , Christensen Christian Kolle , Etter Martin , Ederth Thomas , Sun Licheng , Simak Sergei I. , Abrikosov Igor A. , Gao Feng 
Published: May 2020

AbstractEnvironmentally friendly halide double perovskites with improved stability are regarded as a promising alternative to lead halide perovskites. The benchmark double perovskite, Cs2AgBiBr6, shows attractive optical and electronic features, making it promising for high‐efficiency optoelectronic devices. However, the large band gap limits its further applications, especially for photovoltaics. Herein, we develop a novel crystal‐engineering strategy to significantly decrease the band gap by approximately 0.26 eV, reaching the smallest reported band gap of 1.72 eV for Cs2AgBiBr6 under ambient conditions. The band‐gap narrowing is confirmed by both absorption and photoluminescence measurements. Our first‐principles calculations indicate that enhanced Ag–Bi disorder has a large impact on the band structure and decreases the band gap, providing a possible explanation of the observed band‐gap narrowing effect. This work provides new insights for achieving lead‐free double perovskites with suitable band gaps for optoelectronic applications.
Phosphonate‐Modified UiO‐66 Brønsted Acid Catalyst and Its Use in Dehydra‐Decyclization of 2‐Methyltetrahydrofuran to Pentadienes
Authors: Dorneles de Mello Matheus , Kumar Gaurav , Tabassum Tarnuma , Jain Sheetal K. , Chen Tso‐Hsuan , Caratzoulas Stavros , Li Xinyu , Vlachos Dionisios G. , Han Songi‐I , Scott Susannah L. , Dauenhauer Paul , Tsapatsis Michael 
Published: May 2020

AbstractPhosphorus‐modified all‐silica zeolites exhibit activity and selectivity in certain Brønsted acid catalyzed reactions for biomass conversion. In an effort to achieve similar performance with catalysts having well‐defined sites, we report the incorporation of Brønsted acidity to metal–organic frameworks with the UiO‐66 topology, achieved by attaching phosphonic acid to the 1,4‐benzenedicarboxylate ligand and using it to form UiO‐66‐PO3H2 by post‐synthesis modification. Characterization reveals that UiO‐66‐PO3H2 retains stability similar to UiO‐66, and exhibits weak Brønsted acidity, as demonstrated by titrations, alcohol dehydration, and dehydra‐decyclization of 2‐methyltetrahydrofuran (2‐MTHF). For the later reaction, the reported catalyst exhibits site‐time yields and selectivity approaching that of phosphoric acid on all‐silica zeolites. Using solid‐state NMR and deprotonation energy calculations, the chemical environments of P and the corresponding acidities are determined.
Real‐Time In Vivo Detection of Cellular Senescence through the Controlled Release of the NIR Fluorescent Dye Nile Blue
Authors: Lozano‐Torres Beatriz , Blandez Juan F. , Galiana Irene , García‐Fernández Alba , Alfonso María , Marcos María D. , Orzáez Mar , Sancenón Félix , Martínez‐Máñez Ramón 
Published: May 2020

AbstractIn vivo detection of cellular senescence is accomplished by using mesoporous silica nanoparticles loaded with the NIR‐FDA approved Nile blue (NB) dye and capped with a galactohexasaccharide (S3). NB emission at 672 nm is highly quenched inside S3, yet a remarkable emission enhancement is observed upon cap hydrolysis in the presence of β‐galactosidase and dye release. The efficacy of the probe to detect cellular senescence is tested in vitro in melanoma SK‐Mel‐103 and breast cancer 4T1 cells and in vivo in palbociclib‐treated BALB/cByJ mice bearing breast cancer tumor.
p‐Substituted Tris(2‐pyridylmethyl)amines as Ligands for Highly Active ATRP Catalysts: Facile Synthesis and Characterization
Authors: Enciso Alan E. , Lorandi Francesca , Mehmood Arshad , Fantin Marco , Szczepaniak Grzegorz , Janesko Benjamin G. , Matyjaszewski Krzysztof 
Published: May 2020

AbstractA facile and efficient two‐step synthesis of p‐substituted tris(2‐pyridylmethyl)amine (TPMA) ligands to form Cu complexes with the highest activity to date in atom transfer radical polymerization (ATRP) is presented. In the divergent synthesis, p‐Cl substituents in tris(4‐chloro‐2‐pyridylmethyl)amine (TPMA3Cl) were replaced in one step and high yield by electron‐donating cyclic amines (pyrrolidine (TPMAPYR), piperidine (TPMAPIP), and morpholine (TPMAMOR)) by nucleophilic aromatic substitution. The [CuII(TPMANR2)Br]+ complexes exhibited larger energy gaps between frontier molecular orbitals and >0.2 V more negative reduction potentials than [CuII(TPMA)Br]+, indicating >3 orders of magnitude higher ATRP activity. [CuI(TPMAPYR)]+ exhibited the highest reported activity for Br‐capped acrylate chain ends in DMF, and moderate activity toward C−F bonds at room temperature. ATRP of n‐butyl acrylate using only 10–25 part per million loadings of [CuII(TPMANR2)Br]+ exhibited excellent control.
Potassium Poly(Heptazine Imide): Transition Metal‐Free Solid‐State Triplet Sensitizer in Cascade Energy Transfer and [3+2]‐cycloadditions
Authors: Savateev Aleksandr , Tarakina Nadezda V. , Strauss Volker , Hussain Tanveer , ten Brummelhuis Katharina , Sánchez Vadillo José Manuel , Markushyna Yevheniia , Mazzanti Stefano , Tyutyunnik Alexander P. , Walczak Ralf , Oschatz Martin , Guldi Dirk M. , Karton Amir , Antonietti Markus 
Published: May 2020

AbstractPolymeric carbon nitride materials have been used in numerous light‐to‐energy conversion applications ranging from photocatalysis to optoelectronics. For a new application and modelling, we first refined the crystal structure of potassium poly(heptazine imide) (K‐PHI)—a benchmark carbon nitride material in photocatalysis—by means of X‐ray powder diffraction and transmission electron microscopy. Using the crystal structure of K‐PHI, periodic DFT calculations were performed to calculate the density‐of‐states (DOS) and localize intra band states (IBS). IBS were found to be responsible for the enhanced K‐PHI absorption in the near IR region, to serve as electron traps, and to be useful in energy transfer reactions. Once excited with visible light, carbon nitrides, in addition to the direct recombination, can also undergo singlet–triplet intersystem crossing. We utilized the K‐PHI centered triplet excited states to trigger a cascade of energy transfer reactions and, in turn, to sensitize, for example, singlet oxygen (1O2) as a starting point to synthesis up to 25 different N‐rich heterocycles.
Photocatalytic Fluoro Sulfoximidations of Styrenes
Authors: Wang Chenyang , Tu Yongliang , Ma Ding , Bolm Carsten 
Published: May 2020

AbstractReactions of difluoroiodotoluene with NH‐sulfoximines provide new hypervalent iodine(III) reagents, which photocatalytically transfer a fluoro and a sulfoximidoyl group onto styrenes with high regioselectivity. The substrate scope is broad with respect to both sulfoximines and olefins. Following an operationally simple protocol, a large library of fluorine‐containing N‐functionalized sulfoximines can be accessed. Results from mechanistic investigations revealed the importance of radical intermediates.
Pillar[n]MaxQ: A New High Affinity Host Family for Sequestration in Water
Authors: Xue Weijian , Zavalij Peter Y. , Isaacs Lyle 
Published: May 2020

AbstractWe report the synthesis, X‐ray crystal structure, and molecular recognition properties of pillar[n]arene derivative P[6]AS, which we refer to as Pillar[6]MaxQ along with analogues P[5]AS and P[7]AS toward guests 1–18. The ultratight binding affinity of P[5]AS and P[6]AS toward quaternary (di)ammonium ions renders them prime candidates for in vitro and in vivo non‐covalent bioconjugation, for imaging and delivery applications, and as in vivo sequestration agents.
Nanometer‐sized, rod‐like, ligand‐containing tryptophan complexes: Anion influence–structural geometry–antitumor activity correlations
Authors: El‐Husseiny Amel F. , Hassan Hammed H.A.M. , Fadhil Firas M. , Khalil Tarek E. 
Published: May 2020

AbstractMatrix metalloproteinases (MMPs) are metal‐dependent endopeptidases that are related to the initiation and progression of diseases and are involved in physiological processes such as angiogenesis, wound healing, and embryonic development. Synthetic inhibitors of MMPs are amino acid–based ligands as analyzed by the interactions between the enzyme and its natural substrate. Low production cost and low environmental toxicity of α‐amino acid complexes resulted in a wide pharmacological spectrum, including the anti‐inflammatory and anticonvulsant properties in addition to cytotoxic activities. These facts directed our search for the development of selective inhibitors that contain chemical entity. l‐Tryptophan is a main component of proteins and is essential in human nutrition for establishing and sustaining positive nitrogen balance. Nanomaterials exhibited clinical influence in terms of delivery approaches on bioactive molecules as therapeutic and imaging contrast agents. In this article, we report the synthesis of nanometer rod‐like 2,2′‐(1,3,5,7‐tetraoxopyrrolo[3,4‐f]isoindole‐2,6(1H,3H,5H,7H)‐diyl)bis(3‐(1H‐indol‐3‐yl)propanoic acid) and its metal complexes. The effect of different anions on the geometrical structures and properties of several complexes was studied. Studies indicated that most complexes exhibited dinuclear octahedral or tetrahedral topologies with M–M interaction being absent, whereas mononuclear square planar or square pyramidal topologies were obtained for copper complexes containing chloride or nitrate anions. The ligand exhibited its activity solely against Bacillus subtilis. [Co2(L)Cl2(H2O)2] complex exhibited potent activity against various species of pathogenic microorganisms. The cytotoxicity against MCF‐7 cell line demonstrated that the inhibitory effect is dose dependent. [Cu(HL)Cl.H2O] complex exhibited an interesting cytotoxic activity in addition to copper anticancer analogues, the alternatives to cis‐platin because of their biocompatibility and important roles in biological systems.
Platinum‐Imidazolyl Schiff Base Complexes Immobilized in Periodic Mesoporous Organosilica Frameworks as Catalysts for Hydrosilylation
Authors: Huo Yingpeng , Hu Jiwen , Tu Yuanyuan , Huang Zhenzhu , Lin Shudong , Hu Yangfei , Feng Chao 
Published: May 2020

AbstractAn imidazolyl Schiff base‐containing periodic mesoporous organosilica (PMO) was synthesized via co‐condensation reactions between a newly prepared bis (imidazolyl)imine‐bridged bis silane and tetraethyl orthosilicate in the presence of cetyltrimethyl ammonium bromide as a soft template. The resultant as‐synthesized PMO was then employed as a solid support for platinum catalysts. This complex was fully characterized via various techniques including FTIR, solid‐state13C NMR, and 29Si‐NMR spectroscopy, as well as N2 adsorption/desorption analysis, X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) methods. In addition, the catalyst was proven to efficiently mediate hydrosilylation reactions between olefins and hydrosilanes, and it can be reused for at least five cycles without significant loss of activity.
Impact of ultrasonication on carbon nanotube demixing and damage in polymer nanocomposites
Authors: Iyer Ganapathi Jayadurga , Lee Stephanie S. , Kalyon Dilhan M. , Fisher Frank T. 
Published: May 2020

AbstractWhile ultrasonication is universally employed for dispersion and distribution of carbon nanotubes (CNTs) in a solvent or polymer solution, the current work focuses on the underlying mechanisms of CNT demixing and CNT damage that can occur during processing. Here, multi‐walled CNTs were dispersed in a polycaprolactone polymer matrix using an established solution processing technique. Electrical, rheological, and mechanical characterization results suggest that once nanocomposite property enhancements reach an optimal level, further sonication leads to a decrease in the corresponding properties due to a combination of CNT damage and demixing mechanisms. Evidence of CNT damage from transmission electron microscopy, poor CNT distribution from optical image analysis and shear‐induced crystallization results, and reagglomeration observed from ultraviolet–visible results, taken together, suggest that mechanisms of demixing and damage of the CNTs coexist for excessive sonication times.