bluuebunny/crossref_metadata_2025_split huggingface dataset:
Photoinitiated Transformation of Nanocrystal Superlattice Polymorphs Assembled at a Fluid Interface
Authors: Gao Yingjie , Huang Jen‐Yu , Balazs Daniel M. , Xu Yuanze , Hanrath Tobias 
Published: September 2020

AbstractDirecting the assembly of nanoscale building blocks into programmable superstructures is of broad scientific and technological interest. Advances in nanocrystal self‐assembly at fluid interfaces are combined with digital light processing to demonstrate that how the extent and spatial region of superlattice structure transformation can be controlled. It is shown that the addition of a photoacid generator to the fluid subphase provides new experimental degrees of freedom to modulate the dynamic equilibrium of ligands bound to the colloidal nanocrystal surface. Within the photoexposed regions, the nanocrystal ligand coverage is reduced which impacts the interactions between proximate nanocrystals and drives the transformation from a sixfold to a fourfold symmetric superlattice. Structural analysis is presented from transmission electron microscopy and chemical analysis is presented from infrared spectroscopy to establish the relationship between superlattice structure and ligand coverage. Beyond new insights understanding of and control over deprotection of colloidal nanocrystals at fluid interfaces, the processing method described in this work presents new opportunities to create nanocrystal assemblies with spatially programmable structures.
Poly‐ε‐Lysine or Mel4 Antimicrobial Surface Modification on a Novel Peptide Hydrogel Bandage Contact Lens
Authors: Lace Rebecca , Doherty Kyle G. , Dutta Debarun , Willcox Mark D. P. , Williams Rachel L. 
Published: September 2020

AbstractMicrobial keratitis (MK) is a serious issue in many countries and is often caused by contact lens wear. Antimicrobial peptides (AMPs) are a potentially useful tool for creating antimicrobial surfaces in light of increasing antibiotic resistance. Poly‐ε‐lysine (pεK) is an AMP that has been used extensively as a food preservative and Mel4 has recently been synthesized and studied as an antimicrobial coating for contact lenses. A hydrogel synthesized of pεK cross‐linked with biscarboxylic acids provides a potential lens material which has many surface free amines, that can be subsequently used to attach additional AMPs, creating an antimicrobial lens. The aim of this study is to investigate pεK hydrogels against a clinical strain of Pseudomonas aeruginosa (P. aeruginosa) for preventing or treating MK. Covalent attachment of AMPs is investigated and confirmed by fluorescently tagged peptides. Bound pεK effectively reduces the number of adherent P. aeruginosa in vitro (>3 log). In ex vivo studies positive antimicrobial activity is observed on bare pεK hydrogels and those with additionally bound pεK or Mel4; lenses allow the maintenance of the corneal epithelium. A pεK hydrogel contact lens with additional AMPs can be a therapeutic tool to reduce the incidence of MK.
3D Printing of Core–Shell Capsule Composites for Post‐Reactive and Damage Sensing Applications
Authors: Rupp Harald , Binder Wolfgang H. 
Published: September 2020

Abstract3D printing of multicomponent materials as an advantageous method over traditional mold casting methods is demonstrated, developing small core–shell capsule composites fabricated by a two‐step 3D printing process. Using a two‐print‐head system (fused deposition modeling extruder and a liquid inkjet print head), micro‐sized capsules are manufactured in sizes ranging from 100 to 800 µm. The thermoplastic polymer poly(ε‐caprolactone) (PCL) is chosen as matrix/shell material due to its optimal interaction with the embedded hydrophobic liquids. First, the core–shell capsules are printed with model liquids and pure PCL to optimize the printing parameters and to ensure fully enclosed capsules inside the polymer. As a proof of concept, novel “click” reaction systems, used in self‐healing and stress‐detection applications, are manufactured in which PCL composites with nano‐ and micro‐fillers are combined with reactive, encapsulated liquids. The so generated 3D printed core–shell capsule composite can be used for post‐printing reactions and damage sensing when combined with a fluorogenic dye.
Propargylic Alcohols as Coupling Partners in Transition‐Metal‐Catalyzed Arene C−H Activation
Authors: Kumar Gadi Ranjith , Rajesh Manda , Lin Shuimu , Liu Shouping 
Published: September 2020

AbstractTransition‐metal‐catalyzed site selective arene C−H bond activation concomitant functionalization with various coupling partners gain magnificent attraction in synthetic organic chemistry as complementary to traditional transformations. Mechanistically, these C−H functionalization approaches involve directing group assisted concerted metalation‐deprotonation (CMD), migratory insertion, and reductive elimination sequences. In this realm, diverse categories of coupling partners were employed as C−H functionalization buddies. Particularly alkynes gain enormous attention as annulating agents. These units coordinates with metalcycle through π‐interaction produce annulation outcomes in a straightforward manner. Very recently, propargylic alcohols were appointed as valuable archetypes in arene C−H activation armoury, as they have shown regio‐ and chemoselective migratory insertion into primary metalcycle species via hydroxy chelation. The influential regioselectivity was drawn by dual coordination of metal complexes with the pendent directing group and a propargylic hydroxyl group. In this review, we focused on annulations and functionalization of arenes and propargylic alcohols, which afford intricate cycles as well as complex acyclic motifs in a trouble‐free manner. We categorized these transformations based on number of atoms of propargylic alcohols involved in annulation along with some addition reactions. We anticipate to pave a way towards enhanced endeavours for discovering novel reaction avenues.magnified image
One‐Dimensional π–d Conjugated Coordination Polymer for Electrochromic Energy Storage Device with Exceptionally High Performance
Authors: Cai Guofa , Cui Peng , Shi Wenxiong , Morris Samuel , Lou Shi Nee , Chen Jingwei , Ciou Jing‐Hao , Paidi Vinod K , Lee Kug‐Seung , Li Shuzhou , Lee Pooi See 
Published: September 2020

AbstractThe rational design of previously unidentified materials that could realize excellent electrochemical‐controlled optical and charge storage properties simultaneously, are especially desirable and useful for fabricating smart multifunctional devices. Here, a facile synthesis of a 1D π–d conjugated coordination polymer (Ni‐BTA) is reported, consisting of metal (Ni)‐containing nodes and organic linkers (1,2,4,5‐benzenetetramine), which could be easily grown on various substrates via a scalable chemical bath deposition method. The resulting Ni‐BTA film exhibits superior performances for both electrochromic and energy storage functions, such as large optical modulation (61.3%), high coloration efficiency (223.6 cm2 C−1), and high gravimetric capacity (168.1 mAh g−1). In particular, the Ni‐BTA film can maintain its electrochemical recharge‐ability and electrochromic properties even after 10 000 electrochemical cycles demonstrating excellent durability. Moreover, a smart energy storage indicator is demonstrated in which the energy storage states can be visually recognized in real time. The excellent electrochromic and charge storage performances of Ni‐BTA films present a great promise for Ni‐BTA nanowires to be used as practical electrode materials in various applications such as electrochromic devices, energy storage cells, and multifunctional smart windows.
Teff [Eragrostis tef (Zucc.)] rainfed yield response to planting method, seeding density, and row spacing
Authors: Mihretie Fekremariam , Tsunekawa Atsushi , Bitew Yayeh , Chakelie Gobezie , Derebe Bitwoded , Getahun Wudu , Beshir Omer , Tadesse Zelalem , Asfaw Mitiku 
Published: September 2020

AbstractTeff [Eragrostis tef (Zucc.)] grain yield is low due to lack of improved management practices. We evaluated grain yield and cost of planting methods (broadcast, row, and transplanting), row spacing (10, 15, 20, 25, and 30 cm), and seeding densities (2.5, 5.0, 7.5, 10, 15, 20, and 25 kg ha−1) for teff in the 2012 and 2013 cropping seasons at the Adet Agricultural Research Center farm in northwest Ethiopia. Transplanting (1,675 kg ha−1) resulted in 34 and 75% greater grain yield (P < .05) than row (1,247 kg ha−1) and broadcast planting (958 kg ha−1), respectively. Row planting gave greater (30%) grain yield than broadcasting. Seeding density did not significantly influence grain yield in broadcast or row planting. Row spacing significantly influenced grain yield under row planting but did not significantly influence grain yield under transplanting. Regression analysis indicated grain yield increased as seeding density increased from 2.5 to 10 kg ha−1, then declined at greater seeding densities for both broadcast and row planting. Grain yield declined sharply as row spacing increased from 15 to 30 cm for both transplanting and row planting. Partial‐budget analysis showed that although teff transplanting gave the greatest grain yield, it was not economical due to low straw (biomass) yield and high cost of labor. Row planting at a spacing from 10 to 15 cm at 15 kg seed ha−1 was the most economically effective teff production method, with a net benefit of $1,640 ha−1.
Postoperative pancreatic fistula after gastrectomy for gastric cancer
Authors: Washio Marie , Yamashita Keishi , Niihara Masahiro , Hosoda Kei , Hiki Naoki 
Published: September 2020

AbstractPostoperative pancreatic fistula is one of the most severe complications after gastric cancer surgery, and can cause critical patient conditions leading to surgery‐related death. Fortunately, the incidence of postoperative pancreatic fistula after gastrectomy seems to be decreasing with changes in operative procedures. The rate was reported at about 30% after open gastrectomy with Appleby's method in 1997, but lately has improved below 1% for robotic gastrectomy in 2019. For the diagnosis of postoperative pancreatic fistula, drain amylase concentration has been demonstrated to be beneficial and some reports have proposed the optimal cut‐off values of drain amylase to predict major postoperative pancreatic fistula. There have been many reports identifying risk factors for postoperative pancreatic fistula, including overweight patients, pancreatic anatomy, blunt trauma from compression of the pancreas, and thermal injuries caused by the continuous use of energy devices. And importantly, laparoscopic gastrectomy has been shown to be more often associated with postoperative pancreatic fistula than open gastrectomy in the prospective national clinical database in Japan. Hence, further sophistication of surgical techniques to reduce pancreas compression would have great promise in reducing postoperative pancreatic fistula after laparoscopic gastrectomy.
Injuries during the first hour at work in the U.S. mining industry
Authors: De Sudeshna , Almberg Kirsten S. , Cohen Robert A. , Friedman Lee S. 
Published: September 2020

AbstractBackgroundThe first hour of a shift in a mine is characterized by a large movement of miners from incoming and outgoing shifts, in addition to safety and maintenance checks of mining equipment. These activities rely on communication to ensure a safe transition between shifts. This study aims to identify risk factors for injury among miners during the first hour of a work shift and to characterize injury outcomes.MethodsData from U.S. Mine Safety and Health Administration Part 50 reports, 1983–2015, were used to identify injuries occurring within the first hour of a shift. Multivariable logistic regression was used to evaluate predictors of injuries occurring during the first shift‐hour and to assess the outcome of these injuries.ResultsOut of the 545,537 cases included in the analysis, 16,446 injuries occurred during the first hour of a shift. Risk factors associated with these injuries included being female, being older, working on Sunday and Monday, having an irregular shift start, working night shifts, employed in surface mining operations, and mine operations with <200 employees, and mechanisms of injury related to falls, movement of equipment and personnel, and being struck by or caught between boxes and containers. Injurious incidents occurring during the first hour of work were associated with mass injury events involving five or more workers (aOR = 3.58; 95% CI: 2.77, 4.64).ConclusionsAlthough injury rates were substantially lower during the first hour of work compared to all other work hours, this study identified risk factors and mechanisms of injury that are highly preventable during the first hour of work.
Etiological diagnosis in limb reduction defects and the number of affected limbs: A population‐based study in the Northern Netherlands
Authors: Bergman Jorieke E. H. , Löhner Katharina , van der Sluis Corry K. , Rump Patrick , de Walle Hermien E. K. 
Published: September 2020

AbstractLimb reduction defects (LRDs) that affect multiple limbs are considered to be more often heritable, but only few studies have substantiated this. We aimed to investigate if an etiological diagnosis (genetic disorder or clinically recognizable disorder) is more likely to be made when multiple limbs are affected compared to when only one limb is affected. We used data from EUROCAT Northern Netherlands and included 391 fetuses and children with LRDs born in 1981–2017. Cases were classified as having a transverse, longitudinal (preaxial/postaxial/central/mixed), intercalary, or complex LRD of one or more limbs and as having an isolated LRD or multiple congenital anomalies (MCA). We calculated the probability of obtaining an etiological diagnosis in cases with multiple affected limbs versus one affected limb using relative risk (RR) scores and Fisher's exact test. We showed that an etiological diagnosis was made three times more often when an LRD occurred in multiple limbs compared to when it occurred in one limb (RR 2.9, 95% CI 2.2–3.8, p < 0.001). No genetic disorders were found in isolated cases with only one affected limb, whereas a genetic disorder was identified in 16% of MCA cases with one affected limb. A clinically recognizable disorder was found in 47% of MCA cases with one affected limb. Genetic counseling rates were similar. We conclude that reduction defects of multiple limbs are indeed more often heritable. Genetic testing seems less useful in isolated cases with one affected limb, but is warranted in MCA cases with one affected limb.
Mit der nächsten Generation von Zink‐Bisguanidin‐Polymerisationskatalysatoren zu hochkristallinen, biologisch abbaubaren Polyestern
Authors: Hermann Alina , Hill Stephen , Metz Angela , Heck Joshua , Hoffmann Alexander , Hartmann Laura , Herres‐Pawlis Sonja 
Published: September 2020

AbstractPolylactid und Polycaprolacton sind biologisch abbaubare Polymere, die durch metallkatalysierte Ringöffnungspolymerisation hergestellt werden. Für einen nachhaltigen Lebenszyklus dieser Polymere ist es wichtig, den industriell verwendeten zytotoxischen Katalysator [Sn(Oct)2] durch ungiftige Alternativen zu ersetzen. Wir berichten hier über den schnellsten robusten Katalysator in der Polymerisation von Lactid und ϵ‐Caprolacton. Dieser Zink‐Guanidin‐Katalysator kann unaufgereinigtes technisches rac‐Lactid und ϵ‐Caprolacton in der Schmelze bei verschiedenen [M]/[I]‐Verhältnissen mit schnellen Geschwindigkeitskonstanten, hohen Molmassen und hohen Umsätzen in kurzer Zeit polymerisieren, was zu farblosem, transparentem Polymer führt. Darüber hinaus besitzt durch diesen Komplex hergestelltes Polylactid und Polycaprolacton vorteilhafte hohe Kristallinitäten. Tatsächlich weist das erhaltene Polylactid aufgrund eines höheren Kristallinitätsgrades ein robusteres Abbauprofil auf als sein Sn(Oct)2‐katalysiertes Äquivalent.
Hydroxylamin‐abgeleitetes Reagenz als duales Oxidationsmittel und Aminogruppendonor für die eisenkatalysierte Herstellung von ungeschützten Sulfinamiden aus Thiolen
Authors: Chatterjee Sayanti , Makai Szabolcs , Morandi Bill 
Published: September 2020

AbstractEs wurde eine eisenkatalysierte Reaktion für die selektive Umwandlung von Thiolen (‐SH) in Sulfinamide (‐SONH2) durch direkte Übertragung von ‐O und freien ‐NH2‐Gruppen entwickelt. Die Reaktion läuft unter milden Bedingungen unter Verwendung eines luftstabilen, von Hydroxylamin abgeleiteten Reagenz ab, weist eine breite Toleranz gegenüber funktionellen Gruppen auf, ist skalierbar und verläuft ohne die Verwendung eines Edelmetallkatalysators oder eines zusätzlichen Oxidationsmittels. Diese neuartige, praktische Reaktion führt zur Bildung von zwei verschiedenen neuen Bindungen (S=O und S−N) in einem einzigen Schritt, um chemoselektiv wertvolle, ungeschützte Sulfinamidprodukte zu bilden. Vorläufige mechanistische Studien implizieren die Rolle des alkoholischen Lösungsmittels als Sauerstoffatomdonor.
Gold‐Catalyzed C−H Functionalization Polycondensation for the Synthesis of Aromatic Polymers
Authors: King Eric R. , Tropp Joshua , Eedugurala Naresh , Gonce Lauren E. , Stanciu Sonia , Azoulay Jason D. 
Published: September 2020

AbstractHomogeneous gold (Au) complexes have demonstrated tremendous utility in modern organic chemistry; however, their application for the synthesis of polymers remains rare. Herein, we demonstrate the first catalytic application of Au complexes toward the polycondensation of alkyne‐containing comonomers and heteroarene nucleophiles. Polymerization occurs through successive intermolecular hydroarylation reactions to produce high molecular weight aromatic copolymers with 1,1‐disubstituted alkene backbone linkages. Clear correlations between the rate and degree of polymerization (DP) were established based on catalyst structure and counterion pairing, thus enabling polymerization reactions that proceeded with remarkable efficiency, high reactivity, and exceptional DPs. The reactivity is broad in scope, enabling the copolymerization of highly functionalized aromatic and aliphatic monomers. These results highlight the untapped utility of Au catalysis in providing access to new macromolecular constructs.
Three‐dimensionally cross‐linked styrene‐methyl methacrylate‐divinyl benzene terpolymer networks for organic solvents and crude oil absorption
Authors: Krishnan Mohan Raj , Aldawsari Yazeed Fahad , Alsharaeh Edreese H. 
Published: September 2020

AbstractThe present study reports, high‐performance polymer absorbents for crude oil and organic solvents based on 3D cross‐linked polystyrene‐polymethyl methacrylate/divinyl benzene (PS‐PMMA/DVB). The preparation of the 3D cross‐linked polymer absorbents has been carried out by bulk polymerization method using styrene (S) and methyl methacrylate (MMA) monomers in the presence of DVB with azobisisobutyronitrile as an initiator. The prepared cross‐linked polymer absorbents were characterized by Fourier transform infrared spectroscopy, thermogravimetric and differential scanning calorimetry, and dynamic mechanical analyses. The absorption kinetics, thermodynamics of the absorption process as well as the recyclability of the cross‐linked polymer absorbents were investigated in detail. The developed 3D cross‐linked PS‐PMMA/DVB absorbents have demonstrated excellent absorption capacities for both organic solvents and crude oil. For instance, the developed polymer absorbent (PS‐PMMA/DVB [1 wt%]) shows a maximum absorption capacity of 12 g/g for chloroform, 6 g/g for tetrahydrofuran, and 3 g/g for crude oil. The absorption capacities by the polymer absorbents show a direct relationship with the polarity of the solvents. Moreover, the change of absorption capacity after several repeated cycles of absorption/desorption was only marginal. The demonstrated absorption capacities and the excellent recyclability make polymer absorbents as potential candidates for the oilfield applications and produced water treatments.
Multiomics and Machine Learning Accurately Predict Clinical Response to Adalimumab and Etanercept Therapy in Patients With Rheumatoid Arthritis
Authors: Tao Weiyang , Concepcion Arno N. , Vianen Marieke , Marijnissen Anne C. A. , Lafeber Floris P. G. J. , Radstake Timothy R. D. J. , Pandit Aridaman 
Published: September 2020

ObjectiveTo predict response to anti–tumor necrosis factor (anti‐TNF) prior to treatment in patients with rheumatoid arthritis (RA), and to comprehensively understand the mechanism of how different RA patients respond differently to anti‐TNF treatment.MethodsGene expression and/or DNA methylation profiling on peripheral blood mononuclear cells (PBMCs), monocytes, and CD4+ T cells obtained from 80 RA patients before they began either adalimumab (ADA) or etanercept (ETN) therapy was studied. After 6 months, treatment response was evaluated according to the European League Against Rheumatism criteria for disease response. Differential expression and methylation analyses were performed to identify the response‐associated transcription and epigenetic signatures. Using these signatures, machine learning models were built by random forest algorithm to predict response prior to anti‐TNF treatment, and were further validated by a follow‐up study.ResultsTranscription signatures in ADA and ETN responders were divergent in PBMCs, and this phenomenon was reproduced in monocytes and CD4+ T cells. The genes up‐regulated in CD4+ T cells from ADA responders were enriched in the TNF signaling pathway, while very few pathways were differential in monocytes. Differentially methylated positions (DMPs) were strongly hypermethylated in responders to ETN but not to ADA. The machine learning models for the prediction of response to ADA and ETN using differential genes reached an overall accuracy of 85.9% and 79%, respectively. The models using DMPs reached an overall accuracy of 84.7% and 88% for ADA and ETN, respectively. A follow‐up study validated the high performance of these models.ConclusionOur findings indicate that machine learning models based on molecular signatures accurately predict response before ADA and ETN treatment, paving the path toward personalized anti‐TNF treatment.
Designing Metallogelators Derived from NSAID‐based Zn(II) Coordination Complexes for Drug‐Delivery Applications
Authors: Mondal Swapneswar , Dastidar Parthasarathi 
Published: September 2020

AbstractA crystal engineering approach has been invoked to design a new series of eight Zn(II) coordination complexes derived from various non‐steroidal anti‐inflammatory drugs (NSAIDs), namely diclofenac (DIC), ibuprofen (IBU), naproxen (NAP), flufenamic acid (FLU) and meclofenamic acid (MEC), and two co‐ligands, namely N‐phenyl‐3‐pyridylamide (3‐Py) and N‐phenyl‐4‐pyridylamide (4‐Py), and Zn(NO3)2 as potential supramolecular gelators. Half of the coordination complexes thus synthesized were able to form aqueous gels (MG‐3‐PyMEC, MG‐3‐PyDIC, MG‐4‐PyNAP and MG‐4‐PyMEC). Single‐crystal structures of all eight complexes revealed that they possessed a gelation‐inducing 1D hydrogen‐bonded network including amide…amide synthon in some cases, which supported strongly the design principles based on which these complexes were synthesized. Interestingly, one such metallogelator complex, namely 3‐PyMEC, showed an intriguing anticancer property against a human breast cancer cell line (MDA‐MB‐231), as revealed by both MTT and cell migration assays.