bluuebunny/crossref_metadata_2025 huggingface dataset:
Structure Sorting of Large‐Diameter Carbon Nanotubes by NaOH Tuning the Interactions between Nanotubes and Gel
Authors: Yang Dehua , Hu Jinwen , Liu Huaping , Li Shilong , Su Wei , Li Qian , Zhou Naigen , Wang Yanchun , Zhou Weiya , Xie Sishen , Kataura Hiromichi
Published: August 2017

The structure separation of synthetic single‐wall carbon nanotube (SWCNT) mixture species with diameters larger than 1.2 nm still remains a challenge. Here, an NaOH‐assisted gel chromatography method is used for the structure separation of the SWCNT mixture with a diameter range of 1.2–1.7 nm, in which NaOH is used to tune the interaction between distinct (n, m) SWCNTs and gel. Incrementally increasing NaOH concentration in SWCNT dispersion selectively enhances the adsorbability of different‐structure SWCNTs and enlarges their interaction difference with gel, leading to their structure separation after applying into a gel column system. On this basis, a two‐step method is developed for further improving the structure purity of the separated SWCNTs by combining overloading and stepwise elution. These results are well demonstrated by the optical spectra of the separated SWCNTs. This work paves a way for single‐chirality separation of large‐diameter SWCNTs using gel chromatography technique and is an advanced progress in the structure control of SWCNTs.
Deterministic Nucleation for Halide Perovskite Thin Films with Large and Uniform Grains
Authors: Geske Thomas , Li Junqiang , Worden Matthew , Shan Xin , Chen Mingming , Bade Sri Ganesh R. , Yu Zhibin
Published: August 2017

Halide perovskite materials have come to the forefront of optoelectronics recently owing to their excellent light absorbing and emitting properties. Despite their excellent properties there are still problems that need to be overcome such as short operating lifetimes, and an observed hysteresis behavior in their current–voltage characteristics. It is found that these challenges could be overcome by developing a deterministic nucleation process using gold as a nucleation promoter to control the grain size of the perovskite layer. It is shown that this deterministic nucleation process can be expanded across multiple perovskite systems and can be used to achieve extremely uniform and large grain sizes within the perovskite layer. These large perovskite grains exhibit enhanced stability compared to current state‐of‐the‐art nanocrystalline films, and exhibit no hysteresis in their I–V characteristics which is key if commercialization of perovskites is to be realized.
Substantial Cyano‐Substituted Fully sp2‐Carbon‐Linked Framework: Metal‐Free Approach and Visible‐Light‐Driven Hydrogen Evolution
Authors: Bi Shuai , Lan Zhi‐An , Paasch Silvia , Zhang Wenbei , He Yafei , Zhang Chao , Liu Feng , Wu Dongqing , Zhuang Xiaodong , Brunner Eike , Wang Xinchen , Zhang Fan
Published: August 2017

Polymeric semiconductors are emerging as a kind of competitive photocatalysts for hydrogen evolution due to their well‐tunable structures, versatile functionalization, and low‐cost processibility. In this work, a series of conjugated porous polymers with substantial cyano‐substituted fully sp2‐carbon frameworks are efficiently synthesized by using electron‐deficient tricyanomesitylene as a key building block to promote an organic base‐catalyzed Knoevenagel condensation with various aldehyde‐substituted arenes. The resulting porous polymers feature donor‐acceptor structures with π‐extended conjugation, rendering them with distinct semiconducting properties. They possess hierarchically porous structures, nanoscale morphologies, and intriguing wettability. These promising physical characters, finely tailorable by varying the arene units, are essentially relevant to the abundant cynao substituents over the whole frameworks. The as‐prepared porous polymers exhibit excellent visible‐light‐driven photocatalytic activity for water‐splitting hydrogen evolution with apparent quantum yield up to 2.0% at 420 nm or 1.9% at 470 nm, among the highest values yet reported for porous polymer‐based photocatalysts, also representing the first example of such kinds of catalysts formed through a metal‐free‐catalyzed carbon–carbon coupling reaction.
Hybrid Organic–Inorganic Transition‐Metal Phosphonates as Precursors for Water Oxidation Electrocatalysts
Authors: Zhang Rui , Russo Patrícia A. , Buzanich Ana G. , Jeon Taeyeol , Pinna Nicola
Published: August 2017

Efficient water oxidation catalysts are required for the development of water splitting technologies. Herein, the synthesis of layered hybrid NiFe‐phenylphosphonate compounds from metal acetylacetonate precursors and phenylphosphonic acid in benzyl alcohol, and their oxygen evolution reaction performance in alkaline medium, are reported. The hybrid particles are formed by inorganic layers of NiO6 and FeO6 distorted octahedra separated by bilayers of the organic group, and template the formation in situ of NiFe hydroxide nanosheets of sizes between 5 and 25 nm and thicknesses between 3 and 10 nm. X‐ray absorption spectroscopy measurements suggest that the hybrid also acts as a template for the local structure of the metal sites in the active catalyst, which remain distorted after the transformation. Optimum electrocatalytic activity is achieved with the hybrid compound with a Fe content of 16%. The combination of the synergistic effect between Ni and Fe with the structural properties of the hybrid results in an efficient catalyst that generates a current density of 10 mA cm−2 at an overpotential of 240 mV, and also in a stable catalyst that operates continuously at low overpotentials for 160 h.
Environmentally Benign Halloysite Nanotube Multilayer Assembly Significantly Reduces Polyurethane Flammability
Authors: Smith Ryan J. , Holder Kevin M. , Ruiz Sofia , Hahn Wyatt , Song Yixuan , Lvov Yuri M. , Grunlan Jaime C.
Published: August 2017

In an effort to develop a more environmentally benign flame retardant for polyurethane foam (PUF), layers of halloysite clay nanotubes (HNT) stabilized by branched polyethylenimine (BPEI) or poly(acrylic acid) (PAA) are deposited from aqueous suspensions to create multilayered nanocomposite coatings. PUF is very flammable and widely used in upholstered furniture throughout the world. Foam treated with five BPEI‐HNT/PAA‐HNT bilayers, deposited using layer‐by‐layer assembly, is rendered self‐extinguishing in open flame testing. Cone calorimetry reveals that this coating reduces the peak heat release rate (pkHRR) by 62%. Due to the tubular morphology of HNT, small volatile gasses given off during combustion are trapped, so total smoke release (TSR) is reduced by 60%. Infrared spectroscopy suggests this multilayer film survives during combustion, forming an HNT‐rich barrier that prevents mass and energy transfer during open flame testing and calorimetry. The significant reductions in pkHRR and TSR, along with the self‐extinguishing behavior, indicate that these halloysite‐based multilayer films have the potential to greatly improve PUF fire safety. The low cost and natural abundance of HNT makes this technology especially amenable to widespread use.
Three‐Dimensional Models of the Human Brain Development and Diseases
Authors: Jorfi Mehdi , D'Avanzo Carla , Kim Doo Yeon , Irimia Daniel
Published: August 2017

Deciphering the human brain pathophysiology remains one of the greatest challenges of the 21st century. Neurological disorders represent a significant proportion of diseases burden; however, the complexity of the brain physiology makes it challenging to model its diseases. Simple in vitro models have been very useful for precise measurements in controled conditions. However, existing models are limited in their ability to replicate complex interactions between various cells in the brain. Studying human brain requires sophisticated models to reconstitute the tangled architecture and functions of brain cells. Recently, advances in the development of three‐dimensional (3D) brain cell culture models have begun to recapitulate various aspects of the human brain physiology in vitro and replicate basic disease processes of Alzheimer's disease, amyotrophic lateral sclerosis, and microcephaly. In this review, we discuss the progress, advantages, limitations, and future directions of 3D cell culture systems for modeling the human brain development and diseases.
Light‐Patterned Crystallographic Direction of a Self‐Organized 3D Soft Photonic Crystal
Authors: Zheng Zhi‐Gang , Yuan Cong‐Long , Hu Wei , Bisoyi Hari Krishna , Tang Ming‐Jie , Liu Zhen , Sun Pei‐Zhi , Yang Wei‐Qiang , Wang Xiao‐Qian , Shen Dong , Li Yannian , Ye Fangfu , Lu Yan‐Qing , Li Guoqiang , Li Quan
Published: August 2017

Uniform and patterned orientation of a crystallographic direction of ordered materials is of fundamental significance and of great interest for electronic and photonic applications. However, such orientation control is generally complicated and challenging with regard to inorganic and organic crystalline materials due to the occurrence of uncontrollable dislocations or defects. Achieving uniform lattice orientation in frustrated liquid‐crystalline phases, like cubic blue phases, is a formidable task. Taming and tailoring the ordering of such soft, cubic lattices along predetermined or desired directions, and even imparting a prescribed pattern on lattice orientation, are more challenging, due to the entropy‐domination attribute of soft matter. Herein, we disclose a facile way to realize designed micropatterning of a crystallographic direction of a soft, cubic liquid‐crystal superstructure, exhibiting an alternate uniform and random orientation of the lattice crystallographic direction enabled by a photoalignment technique. Because of the rewritable trait of the photoalignment film, the pattern can be erased and rewritten on‐demand by light. Such an oriented soft lattice sensitively responds to various external stimuli such as temperature, electric field, and light irradiation. Furthermore, advanced reflective photonic applications are achieved based on the patterned crystallographic orientation of the cubic blue phase, soft lattice.
Low‐Noise and Large‐Linear‐Dynamic‐Range Photodetectors Based on Hybrid‐Perovskite Thin‐Single‐Crystals
Authors: Bao Chunxiong , Chen Zhaolai , Fang Yanjun , Wei Haotong , Deng Yehao , Xiao Xun , Li Lingliang , Huang Jinsong
Published: August 2017

Organic–inorganic halide perovskites are promising photodetector materials due to their strong absorption, large carrier mobility, and easily tunable bandgap. Up to now, perovskite photodetectors are mainly based on polycrystalline thin films, which have some undesired properties such as large defective grain boundaries hindering the further improvement of the detector performance. Here, perovskite thin‐single‐crystal (TSC) photodetectors are fabricated with a vertical p–i–n structure. Due to the absence of grain‐boundaries, the trap densities of TSCs are 10–100 folds lower than that of polycrystalline thin films. The photodetectors based on CH3NH3PbBr3 and CH3NH3PbI3 TSCs show low noise of 1–2 fA Hz−1/2, yielding a high specific detectivity of 1.5 × 1013 cm Hz1/2 W−1. The absence of grain boundaries reduces charge recombination and enables a linear response under strong light, superior to polycrystalline photodetectors. The CH3NH3PbBr3 photodetectors show a linear response to green light from 0.35 pW cm−2 to 2.1 W cm−2, corresponding to a linear dynamic range of 256 dB.
Recent Progress on the Development of Metal‐Air Batteries
Authors: Li Lin , Chang Zhi‐wen , Zhang Xin‐Bo
Published: August 2017

The large‐scale electrical energy storage using rechargeable batteries buoys any future success in the global efforts to shift energy usage away from fossil fuels to renewable sources. Compared with other battery technologies, such as Li‐S and LIBs, the metal‐air battery technology holds exceptionally high energy densities and is viewed to be a promising candidate as the energy supplier of the next generation. With the aim to provide easy access to the recent developments of metal‐air batteries and advance their development, this review systematically and comprehensively summarizes, compares and discusses the development of all important kinds of aqueous and/or nonaqueous metal‐air batteries (all in one), based on metal anodes of Li, Na, Zn, Al, from all important aspects, including oxygen electrochemistry, electrocatalyst, transfer/diffusion and interface, electrode and electrolyte materials, and device configuration. As a benefit, our understanding on metal‐air batteries can be deepened and guidance for the development of next generation metal‐air batteries can be provided.
A multi‐sector assessment of community organizational capacity for promotion of Chinese immigrant worker health
Authors: Tsai Jenny H.‐C. , Thompson Elaine A.
Published: August 2017

Background

Community‐based collaborative approaches have received increased attention as a means for addressing occupational health disparities. Organizational capacity, highly relevant to engaging and sustaining community partnerships, however, is rarely considered in occupational health research.

Methods

To characterize community organizational capacity specifically relevant to Chinese immigrant worker health, we used a cross‐sectional, descriptive design with 36 agencies from six community sectors in King County, Washington. Joint interviews, conducted with two representatives from each agency, addressed three dimensions of organizational capacity: organizational commitment, resources, and flexibility. Descriptive statistics were used to capture the patterning of these dimensions by community sector.

Results

Organizational capacity varied widely across and within sectors. Chinese and Pan‐Asian service sectors indicated higher capacity for Chinese immigrant worker health than did Chinese faith‐based, labor union, public, and Pan‐ethnic nonprofit sectors.

Conclusions

Variation in organizational capacity in community sectors can inform selection of collaborators for community‐based, immigrant worker health interventions.
Optimizing Optical Absorption, Exciton Dissociation, and Charge Transfer of a Polymeric Carbon Nitride with Ultrahigh Solar Hydrogen Production Activity
Authors: Zhang Guigang , Li Guosheng , Lan Zhi‐An , Lin Lihua , Savateev Aleksandr , Heil Tobias , Zafeiratos Spiros , Wang Xinchen , Antonietti Markus
Published: August 2017

Polymeric or organic semiconductors are promising candidates for photocatalysis but mostly only show moderate activity owing to strongly bound excitons and insufficient optical absorption. Herein, we report a facile bottom‐up strategy to improve the activity of a carbon nitride to a level in which a majority of photons are really used to drive photoredox chemistry. Co‐condensation of urea and oxamide followed by post‐calcination in molten salt is shown to result in highly crystalline species with a maximum π–π layer stacking distance of heptazine units of 0.292 nm, which improves lateral charge transport and interlayer exciton dissociation. The addition of oxamide decreases the optical band gap from 2.74 to 2.56 eV, which enables efficient photochemistry also with green light. The apparent quantum yield (AQY) for H2 evolution of optimal samples reaches 57 % and 10 % at 420 nm and 525 nm, respectively, which is significantly higher than in most previous experiments.
Benzodisilacyclobutadienes: 8π‐Electron Systems with an Antiaromatic Silicon Ring
Authors: Ishida Shintaro , Misawa Yoshifumi , Sugawara Shohei , Iwamoto Takeaki
Published: August 2017

Benzodisilacyclobutadienes 2 a–c were isolated as blue to green crystalline solids from the reaction of stable disilyne 1 and 1,2‐dibromobenzenes in the presence of potassium graphite. In the solid state, substantial bond alternation was observed within the benzene rings of 2 a–c. In hexane, 2 a–c showed remarkable bathochromic shifts of the π→π* (HOMO→LUMO) absorption bands at 625–670 nm. NMR spectra and theoretical calculations indicated that the diamagnetic ring currents of the benzene rings of 2 a–c are considerably reduced by contributions from the antiaromatic 1,2‐disilacyclobutadienes. In their entirety, the obtained results indicate that 2 a–c represent 8π‐electron systems that contain an antiaromatic 1,2‐disilacyclobutadiene.
Palladium‐Catalyzed [3+3] Annulation of Vinyl Chromium(0) Carbene Complexes through Carbene Migratory Insertion/Tsuji–Trost Reaction
Authors: Wang Kang , Ping Yifan , Chang Taiwei , Wang Jianbo
Published: August 2017

Vinyl chromium(0) Fischer carbene complexes were employed as the source of π‐allylic palladium species for catalytic [3+3] annulation under palladium catalysis. Mechanistically, this transformation is proposed to involve carbene migratory insertion and intramolecular Tsuji–Trost reaction as the key steps. Substituted six‐membered heterocyclic flavonones and quinolines are obtained, depending on the nucleophilic functional group on the coupling partners.
Herpes Zoster and Tofacitinib: Clinical Outcomes and the Risk of Concomitant Therapy
Authors: Winthrop Kevin L. , Curtis Jeffrey R. , Lindsey Stephen , Tanaka Yoshiya , Yamaoka Kunihiro , Valdez Hernan , Hirose Tomohiro , Nduaka Chudy I. , Wang Lisy , Mendelsohn Alan M. , Fan Haiyun , Chen Connie , Bananis Eustratios
Published: August 2017

Objective

Patients with rheumatoid arthritis (RA) are at increased risk of herpes zoster (HZ), and the risk appears to be increased in patients treated with tofacitinib. The aim of this study was to evaluate whether concomitant treatment with conventional synthetic disease‐modifying antirheumatic drugs (csDMARDs) or glucocorticoids (GCs) contributes to the increased risk of HZ in RA patients treated with tofacitinib.

Methods

HZ cases were identified from the databases of 2 phase I, 9 phase II, 6 phase III, and 2 long‐term extension studies of tofacitinib in RA patients. Crude incidence rates (IRs) of all HZ events (serious and nonserious) per 100 patient‐years (with 95% confidence intervals [95% CIs]) were calculated for unique patients. Within phase III studies, we described HZ rates according to concomitant csDMARD treatment and baseline GC use. A multivariable Cox proportional hazards regression model was used to evaluate HZ risk factors across studies.

Results

Across all studies (6,192 patients; 16,839 patient‐years), HZ was reported in 636 tofacitinib‐treated patients (IR 4.0, 95% CI 3.7–4.4). In most cases (93%), HZ was classified as nonserious, and the majority of patients (94%) had involvement of only 1 dermatome. HZ IRs varied across regions, from 2.4 (95% CI 2.0–2.9) in Eastern Europe to 8.0 (95% CI 6.6–9.6) in Japan and 8.4 (95% CI 6.4–10.9) in Korea. Within phase III studies, HZ IRs varied according to tofacitinib dose, background csDMARD treatment, and baseline use of GCs. The IRs were numerically lowest for monotherapy with tofacitinib 5 mg twice daily without GCs (IR 0.56 [95% CI 0.07–2.01]) and highest for tofacitinib 10 mg twice daily with csDMARDs and GCs (IR 5.44 [95% CI 3.72–7.68]). Age, GC use, tofacitinib dose, and enrollment within Asia were independent risk factors for HZ.

Conclusion

Patients receiving treatment with tofacitinib and GCs appear to have a greater risk of developing HZ compared with patients receiving tofacitinib monotherapy without GCs.
Implications of impaired zinc homeostasis in diabetic cardiomyopathy and nephropathy
Authors: Giacconi Robertina , Cai Lu , Costarelli Laura , Cardelli Maurizio , Malavolta Marco , Piacenza Francesco , Provinciali Mauro
Published: August 2017

Impaired zinc homeostasis is observed in diabetes mellitus (DM2) and its complications. Zinc has a specific role in pancreatic β‐cells via insulin synthesis, storage, and secretion. Intracellular zinc homeostasis is tightly controlled by zinc transporters (ZnT and Zip families) and metallothioneins (MT) which modulate the uptake, storage, and distribution of zinc. Several investigations in animal models demonstrate the protective role of MT in DM2 and its cardiovascular or renal complications, while a copious literature shows that a common polymorphism (R325W) in ZnT8, which affects the protein's zinc transport activity, is associated with increased DM2 risk. Emerging studies highlight a role of other zinc transporters in β‐cell function, suggesting that targeting them could make a possible contribution in managing the hyperglycemia in diabetic patients. This article summarizes the current findings concerning the role of zinc homeostasis in DM2 pathogenesis and development of diabetic cardiomyopathy and nephropathy and suggests novel therapeutic targets. © 2017 BioFactors, 43(6):770–784, 2017
Outcomes and readmissions after transcatheter and surgical aortic valve replacement in patients with cirrhosis: A propensity matched analysis
Authors: Dhoble Abhijeet , Bhise Viraj , Nevah Moises I. , Balan Prakash , Nguyen Tom C. , Estrera Anthony L. , Smalling Richard W.
Published: August 2017

Background

The data on the comparative outcomes and readmissions after transcatheter aortic valve replacement (TAVR) and surgical aortic valve replacement (SAVR) in patients with cirrhosis are limited. We compared mortality, complications, discharge disposition, 30‐day readmission rates, length of stay, and cost of hospitalization in cirrhotic patients undergoing TAVR and SAVR.

Methods

The National Inpatient Sample (NIS) and the National Readmission Database (NRD) were used for the study. The International Classification of Diseases‐9th version was used to define cohorts of patients undergoing TAVR and SAVR. Patients undergoing concomitant other valve or coronary bypass surgery were excluded. Propensity‐score matching was used to compare the outcomes between the groups.

Results

From 2012 to 2014, a total of 126 and 157 patients with cirrhosis underwent TAVR and SAVR, respectively. Of the 283 patients, 16 (5.7%) died during the same hospitalization. We found 345 patients with cirrhosis who had undergone an aortic valve replacement (156 with TAVR, and 189 with SAVR) in the 2013 and 2014 NRD. On propensity matching, there were no significant differences between the in‐hospital mortality, readmissions, hospitalization costs, and discharges to home within the TAVR and SAVR groups. However, post‐procedure length of stay (6.3 vs. 10.2 days; P < 0.001) and blood transfusion rates (22% vs. 58%; P < 0.001) were significantly lower in TAVR patients.

Conclusions

Cirrhotic patients undergoing TAVR has high, but similar mortality and 30‐day readmission rates when compared to SAVR; however, has shorter length of stay and lower blood transfusion rates.
Telomerization of 1,3‐Butadiene with Carbon Dioxide: A Highly Efficient Process for δ‐Lactone Generation
Authors: Balbino João M. , Dupont Jairton , Bayón J. Carles
Published: August 2017

A very efficient and selective telomerization of 1,3‐butadiene with CO2 that leads to the δ‐lactone (3‐ethylidene‐6‐vinyltetrahydro‐2H‐pyran‐2‐one) was obtained using palladium acetate and tris(p‐methoxyphenyl)phosphine as a catalyst in the presence of p‐hydroquinone, N,N‐diisopropylethylamine, and acetonitrile. A high turnover number of 4500 with 96 % selectivity to the δ‐lactone was obtained after 5 h reaction at 70 °C. The reaction was deactivated by the presence of different 1,3‐dialkylimidazolium ionic liquids, possibly by the formation of stable and inactive palladium‐imidazole‐2‐ylidene carbenes.
Switching the Cofactor Specificity of an Imine Reductase
Authors: Borlinghaus Niels , Nestl Bettina M.
Published: August 2017

In the last years, imine reductases (IREDs) have gained importance for the formation of chiral amines by catalyzing asymmetric reductions of imines and chemo‐ and stereoselective reductive aminations. However, all characterized members of this steadily growing enzyme family demonstrated strict preference for NADPH, which entails reduced possibilities for efficient cofactor regenerations and limitations in the construction of whole cell systems. To alter the cofactor specificity from NADPH to NADH, we applied the “Cofactor Specificity Reversal—Structural Analysis and Library Design” (CSR‐SALAD) mutagenesis strategy and enlarged the mutant library by further amino acid replacements. This engineering approach has been shown to result in IRED variants with up to 2900‐fold improved NADH/NADPH specificity and completely recovered activity in the reduction of 2‐methyl pyrroline (2MP).
Heterovalent Glycodendrimers as Epitope Carriers for Antitumor Synthetic Vaccines
Authors: Pifferi Carlo , Thomas Baptiste , Goyard David , Berthet Nathalie , Renaudet Olivier
Published: August 2017

The large majority of TACA‐based (TACA=Tumor‐Associated Carbohydrate Antigens) antitumor vaccines target only one carbohydrate antigen, thereby often resulting in the incomplete destruction of cancer cells. However, the morphological heterogeneity of the tumor glycocalix, which is in constant evolution during malignant transformation, is a crucial point to consider in the design of vaccine candidates. In this paper, an efficient synthetic strategy based on orthogonal chemoselective ligations to prepare fully synthetic glycosylated cyclopeptide scaffolds grafted with both Tn and TF antigen analogues is reported. To evaluate their ability to be recognized as tumor antigens, direct interaction ELISA assays have been performed with the anti‐Tn monoclonal antibody 9A7. Although both heterovalent structures showed binding capacities with 9A7, the presence of the second TF epitope did not interfere with the recognition of Tn except in one epitope arrangement. This heterovalent glycosylated structure thus represents an attractive epitope carrier to be further functionalized with T‐cell peptide epitopes.
Mixed Allyl Rare‐Earth Borohydride Complexes: Synthesis, Structure, and Application in (Co‐)Polymerization Catalysis of Cyclic Esters
Authors: Fadlallah Sami , Jothieswaran Jashvini , Capet Frédéric , Bonnet Fanny , Visseaux Marc
Published: August 2017

A series of new trivalent rare‐earth allyl–borohydride complexes with the formula [RE(BH4)2(C3H5)(thf)x] (RE=Sc (1), x=2; RE=Y (2) and La (3), x=3) were synthesized by reaction of the corresponding rare‐earth trisborohydrides [RE(BH4)3(thf)x] with half an equivalent of bis(allyl)magnesium. The complexes were fully characterized by determining their X‐ray structure. Similar to their previously described Nd (4) and Sm (5) analogues, these complexes display a monomeric structure with two terminal trihapto BH4 groups, one π–η3 allyl ligand, three THF molecules for complexes 2 and 3, and two THF molecules for complex 1. The catalytic behavior of complexes 1–5 toward the ring‐opening polymerization (ROP) of l‐lactide (l‐LA) and ϵ‐caprolactone (ϵ‐CL) was assessed. The Nd complex featured the best activity toward l‐LA (turnover frequency (TOF)=1300 h−1) and the order was Nd>La>Sm>Y>Sc. Complexes 1–3 were found very active for the ROP of ϵ‐CL (TOF=166 000 h−1), which is in line with the already established exceptionnally high performance of complexes 4 and 5. With both monomers, it was shown that the borohydride moiety was the preferentially initiating group, rather than the allyl one. The random copolymerization of l‐LA and ϵ‐CL was performed with complexes 1–5, in the absence or in the presence of benzyl alcohol as a chain‐transfer agent, affording copolymers with ϵ‐caprolactone up to 62 % inserted. The copolymers synthesized display a variety of microstructures, that is, blocky, random, or quasi‐alternating.
The Role of Water Distribution Controlled by Transmembrane Potentials in the Cytochrome c–Cardiolipin Interaction: Revealing from Surface‐Enhanced Infrared Absorption Spectroscopy
Authors: Zeng Li , Wu Lie , Liu Li , Jiang Xiue
Published: August 2017

The interaction of cytochrome c (cyt c) with cardiolipin (CL) plays a crucial role in apoptotic functions, however, the changes of the transmembrane potential in governing the protein behavior at the membrane–water interface have not been studied due to the difficulties in simultaneously monitoring the interaction and regulating the electric field. Herein, surface‐enhanced infrared absorption (SEIRA) spectroelectrochemistry is employed to study the mechanism of how the transmembrane potentials control the interaction of cyt c with CL membranes by regulating the electrode potentials of an Au film. When the transmembrane potential decreases, the water content at the interface of the membranes can be increased to slow down protein adsorption through decreasing the hydrogen‐bond and hydrophobic interactions, but regulates the redox behavior of CL‐bound cyt c through a possible water‐facilitated proton‐coupled electron transfer process. Our results suggest that the potential drop‐induced restructure of the CL conformation and the hydration state could modify the structure and function of CL‐bound cyt c on the lipid membrane.
A Trishistidine Pseudopeptide with Ability to Remove Both CuΙ and CuΙΙ from the Amyloid‐β Peptide and to Stop the Associated ROS Formation
Authors: Conte‐Daban Amandine , Boff Bastien , Candido Matias Andreza , Aparicio Claudia N. Montes , Gateau Christelle , Lebrun Colette , Cerchiaro Giselle , Kieffer Isabelle , Sayen Stéphanie , Guillon Emmanuel , Delangle Pascale , Hureau Christelle
Published: August 2017

The pseudopeptide L, derived from a nitrilotriacetic acid scaffold and functionalized with three histidine moieties, is reminiscent of the amino acid side chains encountered in the Alzheimer's peptide (Aβ). Its synthesis and coordination properties for CuΙ and CuΙΙ are described. L efficiently complex CuΙΙ in a square‐planar geometry involving three imidazole nitrogen atoms and an amidate–Cu bond. By contrast, CuΙ is coordinated in a tetrahedral environment. The redox behavior is irreversible and follows an ECEC mechanism in accordance with the very different environments of the two redox states of the Cu center. This is in line with the observed resistance of the CuΙ complex to oxidation by oxygen and the CuΙΙ complex reduction by ascorbate. The affinities of L for CuΙΙ and CuΙ at physiological pH are larger than that reported for the Aβ peptide. Therefore, due to its peculiar Cu coordination properties, the ligand L is able to target both redox states of Cu, redox silence them and prevent reactive oxygen species production by the CuAβ complex. Because reactive oxygen species contribute to the oxidative stress, a key issue in Alzheimer's disease, this ligand thus represents a new strategy in the long route of finding molecular concepts for fighting Alzheimer's disease.
Titanocene Silylpropyne Complexes: Promising Intermediates en route to a Four‐Membered 1‐Metallacyclobuta‐2,3‐diene?
Authors: Reiß Fabian , Reiß Melanie , Spannenberg Anke , Jiao Haijun , Hollmann Dirk , Arndt Perdita , Rosenthal Uwe , Beweries Torsten
Published: August 2017

Coordination of the alkyl‐substituted alkynes Me3SiC2CH2R (1: R=SiMe3; 2: R=N(SiMe3)2) to titanocene centres [Cp′2Ti] (Cp′=Cp, Cp*) yields stable alkyne complexes of the type Cp′2Ti(η2‐Me3SiC2CH2R) (3: Cp′=Cp, R=SiMe3; 5: Cp′=Cp, R=N(SiMe3)2; 6: Cp′=Cp*, R=SiMe3) that are not prone to alkyne/allene isomerisation. When reacting alkyne 2 with Cp*2TiCl2 and Mg formation of the complex Cp*2Ti(III)(η3‐Me3SiC2CH2) (7) which displays a propargylic unit coordinated to the TiIII centre takes place. All complexes were fully characterised, the molecular structures for 5, 6, and 7 are discussed.
Designed Synthesis of Au/Fe3O4@C Janus Nanoparticles for Dual‐Modal Imaging and Actively Targeted Chemo‐Photothermal Synergistic Therapy of Cancer Cells
Authors: Zhang Qi , Zhang Lingyu , Li Shengnan , Chen Xiangjun , Zhang Manjie , Wang Tingting , Li Lu , Wang Chungang
Published: August 2017

Elaborately designed novel multifunctional Janus nanoparticles (JNPs) have attracted considerable attention owing to their anisotropic surface properties and various functionalities that allow them to house several components for the detection and targeting of cancer cells. In this work, we report a novel and facile approach to synthesize Au/Fe3O4@C JNPs, which were further selectively functionalized with amino‐poly(ethylene glycol)thiol (NH2‐PEG‐SH) and folic acid (FA) on the exposed Au domains to achieve high contrast for X‐ray computed tomography (CT) imaging, excellent stability, good biocompatibility, as well as cancer cell‐specific targeting. Meanwhile, the other Fe3O4@C sides with mesoporous structure served as a drug delivery vehicle for doxorubicin (DOX), an efficient photothermal therapy (PTT) agent, and a magnetic resonance (MR) imaging contrast agent. Taking these features together, these unique multifunctional JNPs provide an intriguing nanoplatform for dual‐modal CT and MR imaging‐guided actively targeted chemo‐photothermal synergistic cancer therapy.
Syntheses of Exceptionally Stable Aluminum(III) Metal–Organic Frameworks: How to Grow High‐Quality, Large, Single Crystals
Authors: Guo Yuanyuan , Zhang Jun , Dong Long‐Zhang , Xu Yan , Han Wei , Fang Min , Liu Hong‐Ke , Wu Yong , Lan Ya‐Qian
Published: August 2017

The difficulty of obtaining large single crystals of aluminum carboxylate metal–organic frameworks (MOFs) for structure determinations has limited the development of these water and thermally stable MOFs. Herein, how large single crystals of known MIL‐53(Al) and the first two tetrahedral ligand‐based, visible‐light‐absorbing 3D Al‐MOFs, [Al3(OH)3(HTCS)2] (AlTCS‐1) and [Al5O2(OH)3(TCS)2(H2O)2] (AlTCS‐2; TCS=tetrakis(4‐oxycarbonylphenyl)silane), are obtained in the presence of hydrofluoric or formic acid for conventional single‐crystal diffraction measurements is presented. The technique of obtaining those single crystals has potential to be a general method for obtaining large and good‐quality single crystals of Al‐MOFs. AlTCS‐1 and ‐2 are stable over a wide pH range (1–11), and AlTCS‐1 is even stable in aqua regia solution for at least 24 h. The BET specific surface areas of AlTCS‐1 and ‐2 are 11 and 1506 m2 g−1, respectively. AlTCS‐2 takes up 51 cm3 (STP) g−1 CO2 and 15 cm3 (STP) g−1 CH4 at 298 K and 1 bar, which is relatively high among MOF materials. AlTCS‐1 takes up 30 cm3 g−1 CO2 and 4.2 cm3 g−1 CH4 at 298 K and 1 bar. The rapid and stable photocurrent responses of AlTCS‐1 and ‐2 under UV and visible‐light illumination are observed. Moreover, AlTCS‐1 photocatalyzes the water‐splitting reaction under visible light with an average hydrogen evolution efficiency of 50 μmol g−1 h−1 for the first 10 h in a mixture of water and triethanolamine.
Cognitive Challenges of Changeability: Multi‐Level Flexibility for Operating a Modular Chemical Plant
Authors: Müller Romy , Urbas Leon
Published: August 2017

In changeable modular plants, the goal conflicts implied in adjusting the plant to current demands call for flexible strategy selection by operators on three levels: intervention, decision making, and cognitive meta‐control. The first level refers to making appropriate changes to the system. This requires flexibility on the second level. Flexibility in operators' choice of intervention and decision strategies depends on the third level, which enables a balance between stability and flexibility. The challenges resulting from these flexibility requirements are discussed by reviewing the literature on adaptive decision making and action control in volatile environments.
Pedal peptide/orcokinin‐type neuropeptide signaling in a deuterostome: The anatomy and pharmacology of starfish myorelaxant peptide in Asterias rubens
Authors: Lin Ming , Egertová Michaela , Zampronio Cleidiane G. , Jones Alexandra M. , Elphick Maurice R.
Published: August 2017

Pedal peptide (PP) and orcokinin (OK) are related neuropeptides that were discovered in protostomian invertebrates (mollusks, arthropods). However, analysis of genome/transcriptome sequence data has revealed that PP/OK‐type neuropeptides also occur in a deuterostomian phylum—the echinoderms. Furthermore, a PP/OK‐type neuropeptide (starfish myorelaxant peptide, SMP) was recently identified as a muscle relaxant in the starfish Patiria pectinifera. Here mass spectrometry was used to identify five neuropeptides (ArPPLN1a‐e) derived from the SMP precursor (PP‐like neuropeptide precursor 1; ArPPLNP1) in the starfish Asterias rubens. Analysis of the expression of ArPPLNP1 and neuropeptides derived from this precursor in A. rubens using mRNA in situ hybridization and immunohistochemistry revealed a widespread pattern of expression, with labeled cells and/or processes present in the radial nerve cords, circumoral nerve ring, digestive system (e.g., cardiac stomach) and body wall‐associated muscles (e.g., apical muscle) and appendages (e.g., tube feet and papulae). Furthermore, our data provide the first evidence that neuropeptides are present in the lateral motor nerves and in nerve processes innervating interossicular muscles. In vitro pharmacological tests with SMP (ArPPLN1b) revealed that it causes dose‐dependent relaxation of apical muscle, tube foot and cardiac stomach preparations from A. rubens. Collectively, these anatomical and pharmacological data indicate that neuropeptides derived from ArPPLNP1 act as inhibitory neuromuscular transmitters in starfish, which contrasts with the myoexcitatory actions of PP/OK‐type neuropeptides in protostomian invertebrates. Thus, the divergence of deuterostomes and protostomes may have been accompanied by an inhibitory–excitatory transition in the roles of PP/OK‐type neuropeptides as regulators of muscle activity.
Distribution of tachykinin‐related peptides in the brain of the tobacco budworm Heliothis virescens
Authors: Zhao Xin‐Cheng , Xie Gui‐Ying , Berg Bente G. , Schachtner Joachim , Homberg Uwe
Published: August 2017

Invertebrate tachykinin‐related peptides (TKRPs) comprise a group of signaling molecules having sequence similarities to mammalian tachykinins. A growing body of evidence has demonstrated the presence of TKRPs in the central nervous system of insects. In this investigation, we used an antiserum against locustatachykinin‐II to reveal the distribution pattern of these peptides in the brain of the moth Heliothis virescens. Immunolabeling was found throughout the brain of the heliothine moth. Most of the roughly 500 locustatachykinin‐II immunoreactive cell bodies, that is, ca. 400, were located in the protocerebrum, whereas the rest was distributed in the deutocerebrum, tritocerebrum, and the gnathal ganglion. Abundant immunoreactive processes were located in the same regions. Labeled processes in the protocerebrum were especially localized in optic lobe, central body, lateral accessory lobe, superior protocerebrum, and lateral protocerebrum, while those in the deutocerebrum were present exclusively in the antennal lobe. In addition to brain interneurons, four pairs of median neurosecretory cells in the pars intercerebralis with terminal processes in the corpora cardiaca and aorta wall were immunostained. No sexual dimorphism in immunoreactivity was found. Comparing the data obtained here with findings from other insect species reveals considerable differences, suggesting species‐specific roles of tachykinin‐related peptides in insects.
Rectifiability of Varifolds with Locally Bounded First Variation with Respect to Anisotropic Surface Energies
Authors: De Philippis Guido , De Rosa Antonio , Ghiraldin Francesco
Published: August 2017

We extend Allard's celebrated rectifiability theorem to the setting of varifolds with locally bounded first variation with respect to an anisotropic integrand. In particular, we identify a sufficient and necessary condition on the integrand to obtain the rectifiability of every d‐dimensional varifold with locally bounded first variation and positive d‐dimensional density. In codimension 1, this condition is shown to be equivalent to the strict convexity of the integrand with respect to the tangent plane.© 2017 Wiley Periodicals, Inc.
Highly Efficient Sorption of Methyl Orange by a Metal–Organic Resin–Alginic Acid Composite
Authors: Pournara Anastasia D. , Rapti Sofia , Skliri Euaggelia , Armatas Gerasimos S. , Tsipis Athanassios C. , Manos Manolis J.
Published: August 2017

The composite anion‐exchange material MOR‐1–HA (metal–organic resin‐1–alginic acid) was investigated as sorbent for the capture of the methyl orange anion (MO−) from aqueous solutions. MOR‐1–HA shows a remarkably high sorption capacity (up to 859 mg g−1) and rapid sorption kinetics, the fastest among the reported metal–organic sorbents. It is capable of absorbing MO− over a wide pH range (1–8) and, in addition, it exhibits significant MO− sorption affinity even in the presence of large excesses of competing anions (e.g., Cl−, NO3−, SO42−). The exceptional MO−‐sorption properties of MOR‐1–HA arise not only from its highly porous structure and easily exchangeable Cl− anions, but also from a multitude of interaction effects, such as electrostatic interactions between MO− and the NH3+ groups of the material, hydration/dehydration, hydrophobicity/hydrophilicity, size and capacity of generating lateral interactions, and intercalation as revealed by theoretical studies. An ion‐exchange column with a stationary phase containing MOR‐1–HA and silica sand showed high efficiency for the removal of MO− from various types of aqueous samples. The column can be readily regenerated and reused for many runs with minimal loss (2.3–9.3 %) of its exchange capacity. The simplicity of the MOR‐1–HA/sand column and its high regeneration capability and reusability make it particularly attractive for application in the remediation of MO−‐contaminated industrial wastewater.
Cysticercosis: Reiterating the role of cytodiagnosis
Authors: Pal Shweta , Singh Neha , Chowdhury Nilotpal , Huda Farhanul , Rao Shalinee
Published: August 2017

Background

Cysticercosis is a common parasitic infection in many Asian countries. The histopathological features of this parasitic infection are well established, however, the subtle cytological features and their importance in diagnosing this condition need more elaboration. In this case series we have reiterated the role of fine‐needle aspiration cytology (FNAC) in the diagnosis of cysticercosis in clinically unsuspected cases, thereby obviating the need for a biopsy.

Methods

Sixteen patients presented with palpable subcutaneous swellings. The clinical diagnosis varied from tubercular/reactive lymphadenitis, lipoma to neurofibromatosis. These patients were subjected to FNAC of the swellings.

Result

In all 16 cases, a definitive diagnosis of cysticercosis was made on FNAC on the basis of characteristic features like parasite tegument/bladder wall and occasional hooklets. Features suggestive of host reaction were also observed, which included multinucleated giant cells, mixed inflammatory infiltrate with conspicuous eosinophils, histiocytes, and palisading granulomas. These findings were correlated with histopathology and patients were followed up. We noticed spontaneous resolution of the nodules after the FNAC in six patients.

Conclusion

The cytological diagnosis of cysticercosis is quite straightforward in cases where the actual parasitic structures are identified in the smears. However, in the absence of parasitic fragments, features suggestive of host reaction should alert the cytologist to search for the evidence of cysticercosis in the smear, which can help in early and timely diagnosis and treatment of the disease. We also postulate that injury to certain parts of the larval form during FNAC procedure would result in degeneration of the parasite.
An X‐linked Myh11‐CreERT2 mouse line resulting from Y to X chromosome‐translocation of the Cre allele
Authors: Liao Mingmei , Zhou Junmei , Wang Fen , Ali Yasmin H. , Chan Kelvin L. , Zou Fei , Offermanns Stefan , Jiang Zhisheng , Jiang Zhihua
Published: August 2017

The Myh11‐CreERT2 mouse line (Cre+) has gained increasing application because of its high lineage specificity relative to other Cre drivers targeting smooth muscle cells (SMCs). This Cre allele, however, was initially inserted into the Y chromosome (X/YCre+), which excluded its application in female mice. Our group established a Cre+ colony from male ancestors. Surprisingly, genotype screening identified female carriers that stably transmitted the Cre allele to the following generations. Crossbreeding experiments revealed a pattern of X‐linked inheritance for the transgene (k > 1000), indicating that these female carries acquired the Cre allele through a mechanism of Y to X chromosome translocation. Further characterization demonstrated that in hemizygous X/XCre+ mice Cre activity was restricted to a subset arterial SMCs, with Cre expression in arteries decreased by 50% compared to X/YCre+ mice. This mosaicism, however, diminished in homozygous XCre+/XCre+ mice. In a model of aortic aneurysm induced by a SMC‐specific Tgfbr1 deletion, the homozygous XCre+/XCre+ Cre driver unmasked the aortic phenotype that is otherwise subclinical when driven by the hemizygous X/XCre+ Cre line. In conclusion, the Cre allele carried by this female mouse line is located on the X chromosome and subjected to X‐inactivation. The homozygous XCre+/XCre+ mice produce uniform Cre activity in arterial SMCs.
Towards Ultra‐Bright Gold Nanoclusters
Authors: Cantelli Andrea , Guidetti Gloria , Manzi Jeannette , Caponetti Valeria , Montalti Marco
Published: August 2017

Fluorescence bioimaging is a non‐invasive technique that permits to investigate living organism in real time with high tridimensional resolution. Properly engineered fluorescent (or photoluminescent) nanoparticles promise to surpass conventional fluorescent molecular probes as contrast agent. Photoluminescent semiconductor quantum dots show, for example, enhanced brightness and photostability. Concerns arising from the toxic metal content of quantum dots prompted the search for alternative inorganic nanoparticles with similar properties but less hazardous. Gold is almost unanimously considered to be highly tolerated by living organism and the environment. Nevertheless, although photoluminescence of gold nanocluster is known by decades, brightness of these nanoparticles has typically reported to be low, mostly because of the poor photoluminescence quantum yield (< 1 %). Different approaches have been proposed to enhance this poor quantum yield aiming to achieve ultra‐bright gold nanoparticles with features superior to conventional dyes. Here most relevant and recent results in this direction are summarized and critically discussed.
Sulfenylation of C–H Bonds for C–S Bond Formation under Metal‐Free Conditions
Authors: Dong Dao‐Qing , Hao Shuang‐Hong , Yang Dao‐Shan , Li Li‐Xia , Wang Zu‐Li
Published: August 2017

Sulfenylation of C–H bonds for C–S bond formation under metal‐free conditions has become established as a powerful tool in organic chemistry. Various sulfenylation reagents such as thiols, disulfides, sulfinic acids, and so on have been employed for sulfenynlation reactions. In this review we mainly summarize the recent advances (2014 to the present) in this area and also discuss the mechanisms.