bluuebunny/crossref_metadata_2025 huggingface dataset:
On‐Chip‐Integrated Methylammonium Halide Perovskite Optical Sensors
Authors: Sun Wenzhao , Huang Can , Fan Ruiqin , Liu Shuai , Wang Yujie , Xiao Yun‐Feng , Gan Qiaoqiang , Xiao Shumin , Song Qinghai
Published: January 2019

Label‐free, real‐time, portable, and cost‐effective detection of nanoscale objects is central to early‐stage detection of fatal diseases, environmental monitoring, homeland security, and so on. Owing to their extremely large Q/volume and enhanced light–matter interaction, micro‐ and nanophotonic sensors are intensively studied and their performances are significantly improved. To date, single molecule, single virus, and single nanoparticle have been successfully monitored with microscopic and spectroscopic systems, e.g., high‐Q microcavities and plasmonic devices. However, the current technologies suffer from drawbacks such as instability to ambient vibration, long analyzing time, and high costs. Their widespread uses, especially in portable point‐of‐care devices, are strongly hindered. Herein, taking full advantages of methylammonium lead tri‐halide (MAPbX3) perovskite, the perovskite photodetectors with Si3N4 waveguides are integrated and their potential in on‐chip‐integrated optical sensors is demonstrated. With a simple laser diode, single nanoparticle with radius ≈70 nm is successfully gauged for the first time.
Olefin Oxyamination with Unfunctionalized N‐Alkylanilines
Authors: Gao Shuang , Niggemann Meike
Published: January 2019

N‐Alkylanilines have rarely been used in oxyamination reactions, due to the normally necessary pre‐functionalization of the N‐atom. Also, the formation of aminium radical cations (ARCs) of anilines bearing alkyl substituents is plagued by the ARC's tendency to instantaneously convert to α‐amino radicals or iminium ions. We present a readily available reagent combination that addresses both challenges, and thus allows for an oxyamination with N‐alkylanilines via ARCs as the crucial reactive intermediates and excellent diastereoselectivity.

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Transition Metal‐Free Difunctionalization of C−C Bond with Sodium Sulfinates and Water Leading to (E)‐1‐Phenyl‐4‐sulfonylbut‐1‐enes
Authors: Wang Qiao‐Lin , Chen Zan , Zhou Quan , Zhou Cong‐Shan , Xiong Bi‐Quan , Zhang Pan‐Liang , Yang Chang‐An , Liu Yu , Tang Ke‐Wen
Published: January 2019

Without using any transitionmetal and base, an eco‐friendly, practical and economical protocol has been established for the one‐pot synthesis of diverse (E)‐1‐phenyl‐4‐sulfonylbut‐1‐enes from easily accessible starting materials. This strategy features a wide substrate scope, tolerates a broad range of functional groups, employs a less expensive oxidant, is operationally simple, and can be easily scaled‐up.

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Bromoetherification of Alkenyl Alcohols by Aerobic Oxidation of Bromide: Asymmetric Synthesis of 2‐Bromomethyl 5‐Substituted Tetrahydrofurans
Authors: Tomizuka Akihiko , Moriyama Katsuhiko
Published: January 2019

An asymmetric synthesis of 2‐bromomethyl‐5‐substituted tetrahydrofurans via a chiral‐ruthenium‐catalyzed transfer hydrogenation of 3‐butenyl ketones and bromoetherification of chiral pentenyl alcohols was developed. The inhibition of some side reactions furnished the desired products in high yields with high enantioselectivities. In addition, chiral pentenyl alcohols bearing electron‐donating groups triggered substrate racemization in the aerobic bromoetherification.

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Use of prescription opioid and other drugs among a cohort of persons with Ehlers–Danlos syndrome: A retrospective study
Authors: Schubart Jane R. , Schilling Amber , Schaefer Eric , Bascom Rebecca , Francomano Clair
Published: January 2019

Against the backdrop of increased opioid prescribing in the United States and the associated high rate of side effects, dependence, and addiction, our study examined how opioids and other medications are being used among persons with Ehlers–Danlos syndrome (EDS). EDS is a set of heritable connective tissue disorders with high symptom burden, including chronic pain. Prescription medication use among persons with EDS was compared to a cohort of matched controls using 10 years of administrative claims data from a large database of privately insured patients (2005–2014). Our dataset included 4,294 persons with EDS, ages 5–62 years old. In both adults and children, we found that the percentage of persons with a prescription drug claim was higher in the EDS cohort for all prescription drug classes examined. Among children, opioid use was double in the EDS cohort compared to the control group (27.5% vs. 13.5%); in adults, it was nearly double in EDS patients (62% vs. 34.1%). Among persons who were prescribed opioids, those with EDS had higher cumulative dosages over a 2‐year time period versus controls. Our study aids in understanding opioid and prescription drug use patterns in a vulnerable population with high symptom burden and chronic pain that is often severe.
Von der Natur inspiriertes Wirkstoffdesign: kristallographische Detektion eines selbstgenerierten Inhibitor‐Grundgerüsts
Authors: Gall Flavio M. , Hohl Deborah , Frasson David , Wermelinger Tobias , Mittl Peer R. E. , Sievers Martin , Riedl Rainer
Published: January 2019

Das De‐novo‐Design neuer Wirkstoffmoleküle ist nach wie vor eine anspruchsvolle Aufgabe bei der Suche nach wirksamen und selektiven Modulatoren für therapeutisch relevante Zielproteine. Hier berichten wir über die unerwartete Entdeckung eines peptidischen Liganden 1 durch Röntgenkristallographie, der vom therapeutischen Zielprotein MMP‐13 durch partiellen Selbstabbau generiert wurde, und die anschließende strukturbasierte Optimierung dieses Peptids zu einem hochwirksamen und selektiven β‐Faltblatt‐Peptidmimetikum der endogenen Gewebeinhibitoren von Metalloproteinasen (TIMPs). Der Einbau von nicht‐proteinogenen Aminosäuren in Kombination mit einer Zyklisierungsstrategie erwies sich als entscheidend für das De‐novo‐Design der TIMP‐Peptidmimetika. Das optimierte zyklische Peptid 4 (ZHAWOC7726) ist membrangängig, hat einen IC50‐Wert von 21 nm für MMP‐13 und ein vielversprechendes Selektivitätsprofil bezüglich eines polypharmakologischen Ansatzes mit den Anti‐Krebs‐Zielproteinen MMP‐2 (IC50: 170 nm) und MMP‐9 (IC50: 140 nm).
Synthesis of Benzofuran Derivatives through Cascade Radical Cyclization/Intermolecular Coupling of 2‐Azaallyls
Authors: Deng Guogang , Li Minyan , Yu Kaili , Liu Chunxiang , Liu Zhengfen , Duan Shengzu , Chen Wen , Yang Xiaodong , Zhang Hongbin , Walsh Patrick J.
Published: January 2019

Benzofurans are among the most popular structural units in bioactive natural products, however, the synthesis of such structures by radical cyclization cascade reactions is rare. Herein, we report a mild and broadly applicable method for the construction of complex benzofurylethylamine derivatives through a unique radical cyclization cascade mechanism. Single‐electron transfer (SET) from 2‐azaallyl anions to 2‐iodo aryl allenyl ethers initiates a radical cyclization that is followed by intermolecular radical–radical coupling. This expedient approach enables the synthesis of a range of polycyclic benzofurans that would otherwise be difficult to prepare.
Elusive Zintl Ions [μ‐HSi4]3− and [Si5]2− in Liquid Ammonia: Protonation States, Sites, and Bonding Situation Evaluated by NMR and Theory
Authors: Hastreiter Florian , Lorenz Corinna , Hioe Johnny , Gärtner Stefanie , Lokesh Nanjundappa , Korber Nikolaus , Gschwind Ruth M.
Published: January 2019

The existence of [μ‐HSi4]3− in liquid ammonia solutions is confirmed by 1H and 29Si NMR experiments. Both NMR and quantum chemical calculations reveal that the H atom bridges two Si atoms of the [Si4]4− cluster, contrary to the expectation that it is located at one vertex Si of the tetrahedron. The calculations also indicate that in the formation of [μ‐HSi4]3−, protonation is driven by a high charge density and an increase of electron delocalization compared to [Si4]4−. Additionally, [Si5]2− was detected for the first time and characterized by NMR. Calculations show that it is resistant to protonation, owing to a strong charge delocalization, which is significantly reduced upon protonation. Thus, our methods reveal three silicides in liquid ammonia: unprotonated [Si5]2−, terminally protonated [HSi9]3−, and bridge‐protonated [μ‐HSi4]3−. The protonation trend can be roughly predicted by the difference in charge delocalization between the parent compound and the product, which can be finely tuned by the presence of counter ions in solution.
Dynamic Covalent Bonds in Polymeric Materials
Authors: Chakma Progyateg , Konkolewicz Dominik
Published: January 2019

Dynamic covalent bonds (DCBs) have received significant attention over the past decade. These are covalent bonds that are capable of exchanging or switching between several molecules. Particular focus has recently been on utilizing these DCBs in polymeric materials. Introduction of DCBs into a polymer material provides it with powerful properties including self‐healing, shape‐memory properties, increased toughness, and ability to relax stresses as well as to change from one macromolecular architecture to another. This Minireview summarizes commonly used powerful DCBs formed by simple, often “click” reactions, and highlights the powerful materials that can result. Challenges and potential future developments are also discussed.
Heteroatom‐Doped Porous Carbon Materials with Unprecedented High Volumetric Capacitive Performance
Authors: Jin Huile , Feng Xin , Li Jun , Li Matthew , Xia Yuanzhi , Yuan Yifei , Yang Chao , Dai Bin , Lin Zhiqun , Wang Jichang , Lu Jun , Wang Shun
Published: January 2019

The design of carbon‐based materials with a high mass density and large porosity has always been a challenging goal, since they fulfill the demands of next‐generation supercapacitors and other electrochemical devices. We report a new class of high‐density heteroatom‐doped porous carbon that can be used as an aqueous‐based supercapacitor material. The material was synthesized by an in situ dehalogenation reaction between a halogenated conjugated diene and nitrogen‐containing nucleophiles. Under the given conditions, pyridinium salts can only continue to perform the dehalogenation if there is residue water remaining from the starting materials. The obtained carbon materials are highly doped by various heteroatoms, leading to high densities, abundant multimodal pores, and an excellent volumetric capacitive performance. Porous carbon tri‐doped with nitrogen, phosphorous, and oxygen exhibits a high packing density (2.13 g cm−3) and an exceptional volumetric energy density (36.8 Wh L−1) in alkaline electrolytes, making it competitive to even some Ni‐MH cells.
Readily Available Primary Aminoboranes as Powerful Reagents for Aldimine Synthesis
Authors: Junor Glen P. , Romero Erik A. , Chen Xi , Jazzar Rodolphe , Bertrand Guy
Published: January 2019

Primary aminoboranes (RNHBR2), which are readily available by spontaneous dehydrocoupling of amines and boranes cleanly react at room temperature with aldehydes to give aldimines. The overall transformation from amines to aldimines can be conveniently performed by a sequential one‐pot reaction. This synthetic strategy is especially useful for electron poor and bulky amines which are reluctant to react with aldehydes under dehydration conditions. Using a Glorius robustness screen, we show that this methodology is chemoselective, and functional group tolerant. Computational and experimental data support the irreversible formation of the aldimine product in marked contrast with traditional methods.
Cofactor Controlled Encapsulation of a Rhodium Hydroformylation Catalyst
Authors: Jongkind Lukas J. , Elemans Johannes A. A. W. , Reek Joost N. H.
Published: January 2019

Supramolecular approaches in transition‐metal catalysis, including catalyst encapsulation, have attracted considerable attention. Compared to enzymes, supramolecular catalysts in general are less complex. Enzyme activity is often controlled by the use of smaller cofactor molecules, which is important in order to control reactivity in complex mixtures of molecules. Interested in increasing complexity and allowing control over supramolecular catalyst formation in response to external stimuli, we designed a catalytic system that only forms an efficient supramolecular complex when a small cofactor molecule is added to the solution. This in turn affects both the activity and selectivity when applied in a hydroformylation reaction. This contribution shows that catalyst encapsulation can be controlled by the addition of a cofactor, which affects crucial catalyst properties.
Control Mechanism for cis Double‐Bond Formation by Polyunsaturated Fatty‐Acid Synthases
Authors: Hayashi Shohei , Satoh Yasuharu , Ogasawara Yasushi , Maruyama Chitose , Hamano Yoshimitsu , Ujihara Tetsuro , Dairi Tohru
Published: January 2019

Polyunsaturated fatty acids (PUFAs) such as docosahexaenoic acid (DHA), eicosapentaenoic acid (EPA), and arachidonic acid (ARA) are essential fatty acids for humans. Some microorganisms biosynthesize these PUFAs through PUFA synthases composed of four subunits with multiple catalytic domains. These PUFA synthases each create a specific PUFA without undesirable byproducts, even though the multiple catalytic domains in each large subunit are very similar. However, the detailed biosynthetic pathways and mechanisms for controlling final‐product profiles are still obscure. In this study, the FabA‐type dehydratase domain (DHFabA) in the C‐subunit and the polyketide synthase‐type dehydratase domain (DHPKS) in the B‐subunit of ARA synthase were revealed to be essential for ARA biosynthesis by in vivo gene exchange assays. Furthermore, in vitro analysis with truncated recombinant enzymes and C4‐ to C8‐acyl ACP substrates showed that ARA and EPA synthases utilized two types of DH domains, DHPKS and DHFabA, depending on the carbon‐chain length, to introduce either saturation or cis double bonds to growing acyl chains.
Accordion‐Like Motion in Electrochemically Switchable Crown Ether/Ammonium Oligorotaxanes
Authors: Schröder Hendrik V. , Stein Felix , Wollschläger Jan M. , Sobottka Sebastian , Gaedke Marius , Sarkar Biprajit , Schalley Christoph A.
Published: January 2019

Reversible oxidation reactions in electrochemically switchable oligorotaxanes with tetrathiafulvalene (TTF) decorated 24‐crown‐8 ether wheels generate intramolecular mixed‐valence and radical‐cation interactions between the wheels. This induces shuttling of the wheels and a contraction of inter‐wheel distances. Further oxidation generates repulsive forces between the TTFs and maximizes the inter‐wheel distances instead. These interactions and co‐conformational changes were not observed for structurally similar controls in which acetyl groups along the axle prevent translational motion of the wheels. This operation mode of oligorotaxanes, which is reminiscent of an accordion‐like motion, is promising for functional materials and nanodevices such as piston‐type rotaxane motors.
Filling and coloring effect of pearl shell powder and dye‐loaded pearl shell powder on polypropylene
Authors: Ge Liuqin , Fan Neng , Zhou Youzhou , Xia Meisheng , Ye Ying
Published: January 2019

Dye‐loaded shell powder (DPSP), as a novel filler and pigment, was fabricated from pearl shell powder (PSP) and Direct Red 28. PSP (mean diameter of 1.94 μm) and DPSP (mean diameter of 1.62 μm) were individually incorporated into polypropylene (PP), and the mechanical, crystallization, and color properties of PSP/PP and DPSP/PP composites were investigated. As compared to PSP, DPSP exhibited superior reinforcing and toughening effects on PP, due to the ameliorated filler–polymer interfacial interaction. The optimal additive amount of DPSP was determined as 10 wt %, under which the tensile strength of PP was raised from 33.17 to 35.37 MPa, flexural strength from 41.16 to 44.35 MPa, and impact strength from 3.77 to 5.98 kJ/m2. In comparison with PSP/PP, higher content of β‐PP phase was confirmed in DPSP/PP composites. Furthermore, uniform redness distribution was achieved in DPSP/PP specimens, demonstrating the good coloration performance of DPSP. The results indicated that DPSP can be utilized for coloration and filling modification of polymers. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47455
Synthesis of luminescent polymers in the UV light region from dimethacrylate monomer using novel quinoline dyes
Authors: Alarcon Rafael Turra , dos Santos Giovanny Carvalho , de Oliveira Arthur Rossi , da Silva‐Filho Luiz Carlos , Bannach Gilbert
Published: January 2019

This study aims at thermal and morphological features, as well as the degree of conversion these luminescent polymers obtained using a dimethacrylate monomer, and quinoline dyes as photoinitiator. The photoinitiators provide a fluorescent propriety to the final polymer. Thermal properties such as thermal stability, steps of mass loss, and glass transition are obtained by thermogravimetry‐differential thermal analysis and derivative thermogravimetric and differential scanning calorimetry. Using the mid‐infrared spectroscopy, it is possible to calculate the degree of conversion/rate of polymerization; the data indicate that the quinoline derivatives could be used as photoinitiators in lower concentration (0.1%) resulting in solid rigid polymers with higher conversion (74.24, 71.81, 66.36, and 61.09%). The morphological characteristics of polymers are analyzed by scanning electronic microscopy. Finally, solid ultraviolet–visible (UV–vis) analysis shows a bathochromic shift, due to the stabilization of the molecules in the solid state, compared to liquid UV–vis analysis. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47461.
Comparison of four commonly used high temperature vulcanized silicone rubber formulas for outdoor insulator and their regional adaptability
Authors: Lin Ying , Wang Liming , Yin Fanghui , Farzaneh Masoud , Liu Yuhao , Gao Siming
Published: January 2019

High temperature vulcanized silicone rubber (HTVSR) insulators are widely used in transmission lines. In this article, four formulas [fumed silica and precipitated silica as reinforcing agent, alumina trihydrate (ATH) and alumina as flame retardant, and Fe2O3and Fe3O4as colorant] widely used in the production of HTVSR insulators were investigated by performing a series of laboratory experiments. The surface morphologies of silicone rubber, mechanical characterization (hardness, tensile property, and tear strength), electrical properties (volume resistivity, dielectric property, and breakdown strength), hydrophobicity and its transfer property, and thermal property of these four formulas were analyzed. According to the test results, the formula composed of fumed silica, Fe2O3colorant, and alumina trihydrate (ATH) were excellent in mechanical properties because of more secondary structures, more bound rubber, and uniform dispersion. Therefore, it can be used in strong wind and bird pecking regions. Due to the absence of crystal water, the formula composed of fumed silica, Fe2O3colorant, and alumina was observed to be excellent in thermal stability and electrical properties, making it suitable for the regions with high temperature and humidity. The formula composed of precipitated silica, Fe3O4colorant, and ATH was found to be excellent in hydrophobicity transfer characteristics because of more raw rubber and satisfactory performance could be expected when it was applied in polluted regions. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2019,136, 47477.
Spodoptera litura cyclophilin A is required for Microplitis bicoloratus bracovirus‐induced apoptosis during insect cellular immune response
Authors: Tian Hang‐Yu , Hu Yan , Zhang Pan , Xing Wen‐Xi , Xu Cuixian , Yu Dan , Yang Yang , Luo Kaijun , Li Ming
Published: January 2019

Microplitis bicoloratus bracovirus (MbBV) is a polydnavirus found in the parasitic wasp M. bicoloratus. Although MbBV is a known inducer of apoptosis in host hemocytes, the mechanism by which this occurs remains elusive. In this study, we found that expression of cyclophilin A (CypA) was significantly upregulated in Spodoptera litura hemocytes at 6‐day post‐parasitization. Similar results were reported in High Five cells (Hi5 cells) infected by MbBV, suggesting that the upregulation of CypA is linked to MbBV infection in insect cells. cDNA encoding CypA was cloned from parasitized hemocytes of S. litura, and bioinformatic analyses showed that S. litura CypA belongs to the cyclophilin family of proteins. Overexpression of S. litura CypA in Hi5 cells revealed that the protein promotes MbBV‐induced apoptosis in vitro. Conversely, suppression of the expression and activity of CypA protein significantly rescued the apoptotic phenotype observed in MbBV‐infected Hi5 cells, suggesting that it plays a key role in this process. MbBV infection also promoted the cytoplasmic‐nuclear translocation of CypA in Hi5 cells. Taken together, these results suggest that MbBV infection upregulates the expression of CypA, which is required for MbBV‐mediated apoptosis. Our findings provide insight into the role that CypA plays in insect cellular immune response.
Heberden's Nodes and Knee Osteoarthritis–Related Osseous Structural Damage: Exploratory Study From the Osteoarthritis Initiative
Authors: Haj‐Mirzaian Arya , Mohajer Bahram , Guermazi Ali , Shakoor Delaram , Haugen Ida K. , Roemer Frank W. , Demehri Shadpour
Published: January 2019

Objective

To explore whether Heberden's nodes (HNs) could predict magnetic resonance imaging (MRI)–based knee osteoarthritis (OA)–related osseous structural progression.

Methods

Five hundred seventy‐five subjects from the Foundation for the National Institutes of Health project underwent clinical examination to evaluate HNs at baseline and knee MRI at baseline and 24 months. The MRI was read according to the semiquantitative MRI OA Knee Score and quantitative periarticular bone morphology measures. Adjusted linear/logistic regression models were implemented to assess the association between the presence of HNs at baseline examination and worsening of MRI‐defined osseous structural damage, and odds ratios (ORs) with 95% confidence intervals (95% CIs) were calculated.

Results

Comparing patients with HNs (n = 395) and patients without HNs (n = 180), more periarticular bone area expansion in the knee joint was seen in the patients with HNs over 24 months (adjusted OR [ORadj] 1.39 [95% CI 1.06, 1.83], corrected P [Pcorr] = 0.019), especially in the medial femur (ORadj 1.49 [95% CI 1.05, 2.13], Pcorr = 0.026) and lateral femur (ORadj 2.51 [95% CI 1.58, 3.97], Pcorr < 0.001), femoral notch (ORadj 1.37 [95% CI 1.02, 1.84], Pcorr = 0.04), and lateral trochlea (ORadj 1.44 [95% CI 1.08, 1.9], Pcorr = 0.012). However, a trend toward less osteophyte worsening was seen in patients with HNs in the whole knee joint (ORadj 0.63 [95% CI 0.40, 1.02], Pcorr = 0.058), particularly in the femur region (ORadj 0.54 [95% CI 0.31, 0.95], Pcorr = 0.03), compared to patients without HNs.

Conclusion

The presence of HNs was associated with increased MRI‐based periarticular bone area expansion, but less osteophyte worsening over 24 months in the knee joint, especially in the femoral region.
Identification of Novel Autoantibodies Associated With Psoriatic Arthritis
Authors: Yuan Yulin , Qiu Jingyi , Lin Zuan‐Tao , Li Wen , Haley Christopher , Mui Uyen Ngoc , Ning Jing , Tyring Stephen K. , Wu Tianfu
Published: January 2019

Objective

The autoimmune etiology in psoriasis remains to be clarified. We therefore undertook this study to identify novel pathogenic autoantigens and autoantibodies in patients with psoriasis, with the aim of shedding light on the molecular and cellular basis of the pathogenesis of psoriasis and psoriatic arthritis (PsA).

Methods

In this study, we developed an autoantigen array system that harbors a variety of antigens, including typical autoantigens in rheumatic diseases as well as skin antigens, inflammatory mediators, and putative autoantigens in psoriasis. Serum samples from patients with psoriasis (n = 73) were used to interrogate the antigens on the array. In addition, enzyme‐linked immunosorbent assays of individual autoantibodies were used in validation studies.

Results

Levels of several autoantibodies were found to be elevated in the serum of patients with psoriasis compared to healthy controls; in particular, IgG autoantibodies against 2 novel antigens,LL‐37 andADAMTS‐L5, were significantly increased in patients with psoriasis. Importantly, serum levels of IgG autoantibodies againstLL‐37 andADAMTS‐L5 were correlated with the Psoriasis Area and Severity Index, and reflected disease progression in longitudinally collected serum samples from patients with psoriasis. Importantly, both anti–ADAMTS‐L5 and anti–LL‐37 autoantibody levels were also significantly elevated in psoriasis patients with PsA compared to those without PsA, suggesting that these molecules may be involved in the pathogenesis of PsA.

Conclusion

Our findings indicate that these identified autoantibodies may be useful biomarkers and may serve as therapeutic targets in psoriasis and PsA.
Command filtered path tracking control of saturated ASVs based on time‐varying disturbance observer
Authors: Gao Zhenyu , Guo Ge
Published: January 2019

This paper investigates the path‐tracking control problem for an autonomous surface vessel (ASV) with unknown time‐varying disturbances and input saturation. A robust nonlinear control law is proposed based on a disturbance observer and an auxiliary system in the context of command filtered control. The disturbance observer is constructed to estimate the unknown time‐varying disturbances, the auxiliary dynamic system is employed to handle input saturation, and the compensator based command filtered control technique makes the designed path‐tracking control law simple and easy to implement in practice. It is proved that the nonlinear control law can track the desired vessel's position and heading, while guaranteeing the uniform ultimate boundedness of all signals in the path‐tracking control system. Simulation results further demonstrate the effectiveness of the method.
Fault diagnosis based on sliding mode observer for LPV descriptor systems
Authors: Hamdi Habib , Rodrigues Mickael , Mechmeche Chokri , Benhadj Braiek Naceur
Published: January 2019

This paper considers the problem of fault detection and reconstruction of actuator faults for linear parameter varying descriptor systems. A polytopic sliding mode observer (PSMO) is constructed to achieve simultaneous reconstruction of LPV polytopic descriptor system states and actuator faults. Sufficient conditions for the existence and design algorithm of the proposed polytopic sliding mode observer are provided. In addition, the design of the PSMO is formulated in terms of linear matrix inequalities that can be suitably solved using convex optimization techniques. This PSMO can force the output estimation error to converge to zero in a finite time when the actuators faults are bounded through the reinjection of the output estimation error via a nonlinear switching term. The effectiveness of the design technique is illustrated through a simulation of an anaerobic bioreactor.
Dude, Where's My Rates? Best (and Worst) Practices in Providing Rate Information Online
Authors: Metzler Jake , Teodoro Manuel P.
Published: January 2019

With online access to billing and other customer resources now the rule more than the exception, how well do water and sewer utilities’ websites convey rate information?
Outcomes of infants born to women with influenza A(H1N1)pdm09
Authors: Newsome Kim , Alverson C. J. , Williams Jennifer , McIntyre Anne F. , Fine Anne D. , Wasserman Cathy , Lofy Kathryn H. , Acosta Meileen , Louie Janice K. , Jones‐Vessey Kathleen , Stanfield Valoree , Yeung Alice , Rasmussen Sonja A.
Published: January 2019

Background

Pregnant women with influenza are more likely to have complications, but information on infant outcomes is limited.

Methods

Five state/local health departments collected data on outcomes of infants born to pregnant women with 2009 H1N1 influenza reported to the Centers for Disease Control and Prevention from April to December 2009. Collaborating sites linked information on pregnant women with confirmed 2009 H1N1 influenza, many who were severely ill, to their infants' birth certificates. Collaborators also collected birth certificate data from two comparison groups that were matched with H1N1‐affected pregnancies on month of conception, sex, and county of residence.

Results

490 pregnant women with influenza, 1,451 women without reported influenza with pregnancies in the same year, and 1,446 pregnant women without reported influenza with prior year pregnancies were included. Women with 2009 H1N1 influenza admitted to an intensive care unit (ICU; n = 64) were more likely to deliver preterm infants (<37 weeks), low birth weight infants, and infants with Apgar scores <=6 at 5 min than women in comparison groups (adjusted relative risk, aRR = 3.9 [2.7, 5.6], aRR = 4.6 [2.9, 7.5], and aRR = 8.7 [3.6, 21.2], for same year comparisons, respectively). Women with influenza who were not hospitalized and hospitalized women not admitted to the ICU did not have significantly elevated risks for adverse infant outcomes.

Conclusions

Severely ill women with 2009 H1N1 influenza during pregnancy were more likely to have adverse birth outcomes than women without influenza, providing more support for influenza vaccination during pregnancy.
Lessons for all from the early years of the global surgery initiative
Authors: Wladis A , Roy N , Löfgren J
Published: January 2019

Six elements for future success
Allele‐Specific Inhibition of Histone Demethylases
Authors: Wagner Shana , Waldman Megan , Arora Simran , Wang Sinan , Scott Valerie , Islam Kabirul
Published: January 2019

Histone demethylases play a critical role in mammalian gene expression by removing methyl groups from lysine residues in degree‐ and site‐specific manner. To specifically interrogate members and isoforms of this class of enzymes, we have developed demethylase variants with an expanded active site. The mutant enzymes are capable of performing lysine demethylation with wild‐type proficiency, but are sensitive to inhibition by cofactor‐competitive molecules embellished with a complementary steric “bump”. The selected inhibitors show more than 20‐fold selectivity over the wild‐type demethylase, thus overcoming issues typical to pharmacological and genetic approaches. The mutant–inhibitor pairs are shown to act on a physiologically relevant full‐length substrate. By engineering a conserved amino acid to achieve member‐specific perturbation, this study provides a general approach for studying histone demethylases in diverse cellular processes.
Insight into the Structure and Activity of Surface‐Engineered Lipase Biofluids
Authors: Zhou Ye , Jones Nykola C. , Nedergaard Pedersen Jannik , Pérez Bianca , Vrønning Hoffmann Søren , Vang Petersen Steen , Skov Pedersen Jan , Perriman Adam , Kristensen Peter , Gao Renjun , Guo Zheng
Published: January 2019

Despite a successful application of solvent‐free liquid protein (biofluids) concept to a number of commercial enzymes, the technical advantages of enzyme biofluids as hyperthermal stable biocatalysts cannot be fully utilized as up to 90–99% of native activities are lost when enzymes were made into biofluids. With a two‐step strategy (site‐directed mutagenesis and synthesis of variant biofluids) on Bacillus subtilis lipase A (BsLA), we elucidated a strong dependency of structure and activity on the number and distribution of polymer surfactant binding sites on BsLA surface. Here, it is demonstrated that improved BsLA variants can be engineered via site‐mutagenesis by a rational design, either with enhanced activity in aqueous solution in native form, or with improved physical property and increased activity in solvent‐free system in the form of a protein liquid. This work answered some fundamental questions about the surface characteristics for construction of biofluids, useful for identifying new strategies for developing advantageous biocatalysts.
Why play? Thoughts on evidence‐based treatments and why play therapy is still relevant
Authors: Boyle‐Toledo Kiera
Published: January 2019

In the current age of managed care and evidence‐based treatments, play therapy has declined in popularity and prestige. Other treatments offer more concrete techniques and means of achieving measurable outcomes. They have been studied using randomized clinical trials, providing solid evidence that they are effective at treating particular diagnoses and symptoms. Although some preliminary evidence exists to back play therapy as an effective treatment for certain presenting problems, it lacks the evidence base of other treatments. Why, then, do child therapists still use play therapy?
ADHD/ASD in families: Sibling study shows differences and similarities of disorders
Authors: Knopf Alison
Published: January 2019

Younger siblings of children with autism spectrum disorder (ASD) or attention‐deficit/hyperactivity disorder (ADHD) are at elevated risk for the same disorder, but, additionally, at risk of the other disorder as well, researchers have found. Their study helps support the idea that there are shared genetic mechanisms underlying both disorders. The researchers urge screening and early detection, as well as efforts at understanding potential shared causes of both disorders.
Posterior polar annular choroidal dystrophy association with cystoid macular edema
Authors: Del Valle‐Nava Fernando , Sánchez‐Ramos Jorge , Hernández‐Vázquez Angeles , Gonzalez‐Saldivar Gerardo , Ramirez‐Estudillo Abel
Published: January 2019

Key Clinical Message

Posterior polar annular choroidal dystrophy (PPACD) is an uncommon retinal dystrophy causing nyctalopia. PPACD has been characteristically described as a foveal sparing dystrophy. We report the first case with cystoid macular edema association.
Incisional hernia repair with plication and utilization of Botox injections: First case report from Saudi Arabia for a 19‐year‐old female
Authors: Hijji Talal , AlShammari Abdullah , AlHammad Alanoud , AlKhalefah Ghadah , Hashem Fuad , Almomen Salha , Aburahmah Mohammad
Published: January 2019

Key Clinical Message

This article reports on the use of Botox preoperatively for the treatment of a complex ventral hernia which would have typically been treated with component separation technique. The case demonstrates that using the recently developed technique can aid in performing a tension‐free hernia repair with potentially lower complication and recurrence rates.
Redox‐Reversible 2D Metal–Organic Framework Nanosheets (MONs) Based on the Hydroquinone/Quinone Couple
Authors: Maka Vijay Kumar , Mukhopadhyay Arindam , Jindal Swati , Moorthy Jarugu Narasimha
Published: January 2019

2D metal–organic nanosheets (MONs), akin to graphene, have aroused immense contemporary interest. In our quest to develop functional 2D MONs based on organic linkers designed de novo, we reasoned that benzene‐tetrabenzoic acid, which has been exploited tremendously in the construction of pillared metal–organic frameworks (MOFs), could be maneuvered readily to access redox‐active MONs based on the benzoquinone/hydroquinone redox couple. Herein, we show that the self‐assembly of 2,3,5,6‐tetrakis(p‐carboxyphenyl)hydroquinone H4BTA with Zn(NO3)2 does lead to 2D metal–organic nanosheets that stack down the y axis, affording a layered Zn MOF. Although the crystals of the latter do not exhibit a discernible chemically induced redox switching behavior, the 2D MONs accessed by ultrasound‐induced liquid‐phase exfoliation (UILPE) lend themselves to a facile redox switching behavior. Treatment of a dispersion of the 2D MONs in methanol with phenyliodine(III) diacetate (PIDA) results in the oxidation of the hydroquinone core to benzoquinone. Remarkably, the latter can be reverted to the former by treatment with ascorbic acid as a reducing agent; indeed, the redox process can be made out by the naked eye. The results constitute the first example of chemically induced redox switching of 2D MONs. In view of emergent applications of 2D materials in general and MONs in particular, for example, improvement of the performance of membranes in separations by doping with MONs, the redox‐switchable property may lead to the development of unique materials with heretofore unexplored potential.
Guest‐Selective Recognition in a Flexible Bipyridinium‐Based Framework in a Reversible Crystal‐to‐Crystal Fashion
Authors: Tan Bin , Yang Xiao‐Dong , Sun Li , Huang Xiao‐Ying , Zhang Jie
Published: January 2019

A flexible bipyridinium‐linker‐based porous host framework with electron‐accepting pore surface, namely, [Zn2(L)(pmc)1.5]⋅12 H2O (1; L⋅Cl2=1,1′‐[1,4‐phenylene‐bis(methylene)]bis(4,4′‐bipyridinium) dichloride, H4pmc=pyromellitic acid) exhibits recognition of phenol and aromatic amine guests based on adsorbent–adsorbate charge‐transfer interactions. Significantly, the resultant guest‐encapsulated complexes 1@Guests can all be characterized by single‐crystal X‐ray diffraction. The host framework undergoes a reversible single crystal‐to‐single crystal transformation in response to the inclusion of different guests with flexible torsional motions of the hexagonal ring and the trapezoid‐shaped bipyridinium groups. Such recognition can be visibly monitored and detected by obvious color changes. The host framework could also be recovered, and this suggested that guest sorption/desorption is reversible and that the host framework could be reused in potential applications. This work may provide an effective way to develop porous materials with special emphasis on applications involving guest recognition.
Regulating Charge‐Transfer in Conjugated Microporous Polymers for Photocatalytic Hydrogen Evolution
Authors: Mothika Venkata Suresh , Sutar Papri , Verma Parul , Das Shubhajit , Pati Swapan K. , Maji Tapas Kumar
Published: January 2019

Bandgap engineering in donor–acceptor conjugated microporous polymers (CMPs) is a potential way to increase the solar‐energy harvesting towards photochemical water splitting. Here, the design and synthesis of a series of donor–acceptor CMPs [tetraphenylethylene (TPE) and 9‐fluorenone (F) as the donor and the acceptor, respectively], F0.1CMP, F0.5CMP, and F2.0CMP, are reported. These CMPs exhibited tunable bandgaps and photocatalytic hydrogen evolution from water. The donor–acceptor CMPs exhibited also intramolecular charge‐transfer (ICT) absorption in the visible region (λmax=480 nm) and their bandgap was finely tuned from 2.8 to 2.1 eV by increasing the 9‐fluorenone content. Interestingly, they also showed emissions in the 540–580 nm range assisted by the energy transfer from the other TPE segments (not involved in charge‐transfer interactions), as evidenced from fluorescence lifetime decay analysis. By increasing the 9‐fluorenone content the emission color of the polymer was also tuned from green to red. Photocatalytic activities of the donor–acceptor CMPs (F0.1CMP, F0.5CMP, and F2.0CMP) are greatly enhanced compared to the 9‐fluorenone free polymer (F0.0CMP), which is essentially due to improved visible‐light absorption and low bandgap of donor–acceptor CMPs. Among all the polymers F0.5CMP with an optimum bandgap (2.3 eV) showed the highest H2 evolution under visible‐light irradiation. Moreover, all polymers showed excellent dispersibility in organic solvents and easy coated on the solid substrates.
Fullerene‐Filled Stilbene Stars: The Balance between Isolated C60 Helices and 3D Networks in Liquid‐Crystal Self‐Assemblies
Authors: Hügel Markus , Dechant Moritz , Scheuring Nikolai , Ghosh Tapas , Lehmann Matthias
Published: January 2019

A series of shape‐persistent star‐shaped oligo(phenylene vinylene) liquid crystals and derivatives with fullerene tethered through spacers of different lengths to one arm were successfully synthesized. Solution studies by NMR, UV/Vis and fluorescence spectroscopy revealed the preferential location of the C60 acceptor in the vicinity of the peripheral donor unit, which affects the quenching of the emission of the conjugated stilbenoid scaffold in the donor–acceptor dyad. The fluorescence was completely absent in the liquid crystal phase due to the extraordinary hierarchical self‐assembly. In this family of mesogens, the intrinsic free space has to be filled either by an extremely tight packing of the stars or by the fullerenes as guests. The spacer lengths control the nanosegregation of the C60 units in the cavities of the stars in either independent triple helices or unprecedented 3D networks, in which fullerenes are positioned at the interface of neighboring columns. Eventually, the clearing temperature of such large complex donor–acceptor systems can be tuned by an entropy effect defined by the length of the spacer. The accessibility of the isotropic phase without decomposition is an important prerequisite for future alignment studies associated with potential material applications in organic electronics.
Dendrimeric Nanoparticles for Two‐Photon Photodynamic Therapy and Imaging: Synthesis, Photophysical Properties, Innocuousness in Daylight and Cytotoxicity under Two‐Photon Irradiation in the NIR
Authors: Sourdon Aude , Gary‐Bobo Magali , Maynadier Marie , Garcia Marcel , Majoral Jean‐Pierre , Caminade Anne‐Marie , Mongin Olivier , Blanchard‐Desce Mireille
Published: January 2019

The synthesis and the photophysical properties of a new class of fully organic monodisperse nanoparticles for combined two‐photon imaging and photodynamic therapy are described. The design of such nanoparticles is based on the covalent immobilization of a dedicated quadrupolar dye that combines excellent two‐photon absorbing (2PA) properties, fluorescence and singlet oxygen generation ability, in a phosphorous‐based dendrimeric architecture. First, a bifunctional quadrupolar dye bearing two different grafting moieties, a phenol function and an aldehyde function, was synthesized. It was then covalently grafted through its phenol function to a phosphorus‐based dendrimer scaffold of generation 1. The remaining aldehyde functions were then used to continue the dendrimer synthesis up to generation 2, introducing finally 24 water‐solubilizing triethyleneglycol chains at its periphery. A dendrimer confining 12 photoactive quadrupolar units in its inner scaffold and showing water solubility was thus obtained. Interestingly, the G1 and G2 dendrimers retain some fluorescence as well as significant singlet oxygen production efficiencies while they were found to show very high 2PA cross‐sections in a broad range of the NIR biological spectral window. Hydrophilic dendrimer G2 was tested in vitro on breast cancer cells, first in one‐ and two‐photon microscopy, which allowed for visualization of their cell internalization, then in two‐photon photodynamic therapy. While being nontoxic in the dark and, more importantly, under exposure to daylight, dendrimer G2 proved to be a very efficient cell‐death inducer only under two‐photon irradiation in the NIR.
A New Biscarbazole‐Based Metal–Organic Framework for Efficient Host–Guest Energy Transfer
Authors: Mu Qianqian , Liu Jingjuan , Chen Weiben , Song Xiaoyu , Liu Xiaoting , Zhang Xiaotao , Chang Ze , Chen Long
Published: January 2019

A new metal–organic framework (MOF), [Zn6L4(Me2NH2+)4⋅3 H2O] (1) was constructed based on [9, 9′‐biscarbazole]‐3, 3′, 6, 6′‐tetracarboxylic acid (H4L) and Zn2+ ions. The porous framework and intense blue fluorescence of the MOF based on the biscarbazole moiety of the ligand could facilitate efficient host to guest energy transfer, which makes it an ideal platform for the tuning of luminescence.
Development, Scope, and Applications of Titanium(III)‐Catalyzed Cyclizations to Aminated N‐Heterocycles
Authors: Leijendekker Leonardus H. , Weweler Jens , Leuther Tobias M. , Kratzert Daniel , Streuff Jan
Published: January 2019

The exceptionally mild conditions of a titanium(III)‐catalyzed cyclization reaction paired with a convenient acid/base extraction have enabled the straightforward synthesis, isolation, and direct N‐functionalization of amino heterocycles such as 3‐aminoindoles and ‐pyrroles. The unprotected heterocycles are ideal building blocks for the installation of aminated indoles and pyrroles into target molecules, but their sensitivity has previously impeded their synthesis by modern catalytic methods. This full paper presents the development and extended scope of the new cyclization methodology. The transformation of the products into fused bis‐indoles is also demonstrated along with the discovery of an unusual palladium‐catalyzed reductive biphenyl coupling reaction. The titanium(III)‐catalyzed cyclization has also been applied to the synthesis of substituted 3‐iminoindolines, which are of potential interest for applications in natural product synthesis and exhibit tunable blue‐to‐green fluorescence properties.
Iodide Discrimination by Tetra‐Iodotriazole Halogen Bonding Interlocked Hosts
Authors: Klein Harry A. , Beer Paul D.
Published: January 2019

Whilst the exploitation of interlocked host frameworks for anion recognition is widely established, examples incorporating halogen bond donor groups are still relatively rare. Through the integration of a novel tetra(iodotriazole)‐pyridinium motif into macrocycle and axle components, a family of halogen bonding catenane and rotaxanes are constructed for anion recognition studies in a competitive aqueous‐organic solvent mixture. Importantly, the degree of anion selectivity displayed is dictated by the topological nature and charged state of the respective interlocked host cavity. All the interlocked hosts exhibit iodide anion selectivity over other halides and sulfate, with the level of discrimination being the greatest with the mono‐cationic rotaxane. Arising from greater electrostatic interactions working in tandem with halogen bonding and hydrogen bonding, the di‐cationic rotaxane displays stronger anion association at the expense of a relatively lower degree of iodide selectivity.
Cellular Target of a Rhodium Metalloinsertor is the DNA Base Pair Mismatch
Authors: Boyle Kelsey M. , Nano Adela , Day Catherine , Barton Jacqueline K.
Published: January 2019

Defects in DNA mismatch repair (MMR) are commonly found in various cancers, especially in colorectal cancers. Despite the high prevalence of MMR‐deficient cancers, mismatch‐targeted therapeutics are limited and diagnostic tools are indirect. Here, we examine the cytotoxic properties of a rhodium metalloinsertor, [Rh(phen)(chrysi)(PPO)]2+ (RhPPO) in 27 diverse colorectal cancer cell lines. Despite the low frequency of genomic mismatches and the non‐covalent nature of the RhPPO‐DNA lesion, RhPPO is on average five times more potent than cisplatin. Importantly, the biological target and profile for RhPPO differs from that of cisplatin. A fluorescent metalloinsertor, RhCy3, was used to demonstrate that the cellular target of RhPPO is the DNA mismatch. RhCy3 represents a direct probe for MMR‐deficiency and correlates directly with the cytotoxicity of RhPPO across different cell lines. Overall, our studies clearly indicate that RhPPO and RhCy3 are promising anticancer and diagnostic probes for MMR‐deficient cancers, respectively.
Digitalization in Thermodynamics
Authors: Forte Esther , Jirasek Fabian , Bortz Michael , Burger Jakob , Vrabec Jadran , Hasse Hans
Published: January 2019

Digitalization is about data and how they are used. This has always been a key topic in applied thermodynamics. In the present work, the influence of the current wave of digitalization on thermodynamics is analyzed. Thermodynamic modeling and simulation is changing as large amounts of data of different nature and quality become easily available. The power and complexity of thermodynamic models and simulation techniques is rapidly increasing, and new routes become viable to link them to the data. Machine learning opens new perspectives, when it is suitably combined with classical thermodynamic theory. Illustrated by examples, different aspects of digitalization in thermodynamics are discussed: strengths and weaknesses as well as opportunities and threats.