bluuebunny/crossref_metadata_2025 huggingface dataset:
A Supercompressible, Elastic, and Bendable Carbon Aerogel with Ultrasensitive Detection Limits for Compression Strain, Pressure, and Bending Angle
Authors: Zhuo Hao , Hu Yijie , Tong Xing , Chen Zehong , Zhong Linxin , Lai Haihong , Liu Linxiang , Jing Shuangshuang , Liu Qingzhong , Liu Chuanfu , Peng Xinwen , Sun Runcang
Published: March 2018

Ultralight and compressible carbon materials have promising applications in strain and pressure detection. However, it is still difficult to prepare carbon materials with supercompressibility, elasticity, stable strain–electrical signal response, and ultrasensitive detection limits, due to the challenge in structural regulation. Herein, a new strategy to prepare a reduced graphene oxide (rGO)‐based lamellar carbon aerogels with unexpected and integrated performances by designing wave‐shape rGO layers and enhancing the interaction among the rGO layers is demonstrated. Addition of cellulose nanocrystalline and low‐molecular‐weight carbon precursors enhances the interaction among rGO layers and thus produces an ultralight, flexible, and superstable structure. The as‐prepared carbon aerogel displays a supercompressibility (undergoing an extreme strain of 99%) and elasticity (100% height retention after 10 000 cycles at a strain of 30%), as well as stable strain–current response (at least 10 000 cycles). Particularly, the carbon aerogel is ultrasensitive for detecting tiny change in strain (0.012%) and pressure (0.25 Pa), which are the lowest detection limits for compressible carbon materials reported in the literature. Moreover, the carbon aerogel exhibits excellent bendable performance and can detect an ultralow bending angle of 0.052°. Additionally, the carbon aerogel also demonstrates its promising application as wearable devices.
Implantable Synthetic Immune Niche for Spatiotemporal Modulation of Tumor‐Derived Immunosuppression and Systemic Antitumor Immunity: Postoperative Immunotherapy
Authors: Phuengkham Hathaichanok , Song Chanyoung , Um Soong Ho , Lim Yong Taik
Published: March 2018

The development of biomaterial‐based immune niches that can modulate immunosuppressive factors in tumor microenvironment (TME) will be a key technology for improving current cancer immunotherapy. Here, implantable, engineered 3D porous scaffolds are designed to generate synergistic action between myeloid‐derived suppressor cell (MDSC)‐depleting agents, which can accommodate the establishment of a permissive immunogenic microenvironment to counteract tumor‐induced immunosuppression, and cancer vaccines consisting of whole tumor lysates and nanogel‐based adjuvants, which can generate tumor antigen‐specific T cell responses. The local peritumoral implantation of the synthetic immune niche (termed immuneCare‐DISC, iCD) as a postsurgical treatment in an advanced‐stage primary 4T1 breast tumor model generates systemic antitumor immunity and prevents tumor recurrence at the surgical site as well as the migration of residual tumor cells into the lungs, resulting in 100% survival. These therapeutic outcomes are achieved through the inhibition of immunosuppressive MDSCs in tumors and spleens by releasing gemcitabine and recruitment/activation of dendritic cells, enhanced population of CD4+ and CD8+ T cells, and increased IFN‐γ production by cancer vaccines from the iCD. This combined spatiotemporal modulation of tumor‐derived immunosuppression and vaccine‐induced immune stimulation through the iCD is expected to provide an immune niche for prevention of postoperative tumor recurrence and metastasis.
Unique Bond Breaking in Crystalline Phase Change Materials and the Quest for Metavalent Bonding
Authors: Zhu Min , Cojocaru‐Mirédin Oana , Mio Antonio M. , Keutgen Jens , Küpers Michael , Yu Yuan , Cho Ju‐Young , Dronskowski Richard , Wuttig Matthias
Published: March 2018

Laser‐assisted field evaporation is studied in a large number of compounds, including amorphous and crystalline phase change materials employing atom probe tomography. This study reveals significant differences in field evaporation between amorphous and crystalline phase change materials. High probabilities for multiple events with more than a single ion detected per laser pulse are only found for crystalline phase change materials. The specifics of this unusual field evaporation are unlike any other mechanism shown previously to lead to high probabilities of multiple events. On the contrary, amorphous phase change materials as well as other covalently bonded compounds and metals possess much lower probabilities for multiple events. Hence, laser‐assisted field evaporation in amorphous and crystalline phase change materials reveals striking differences in bond rupture. This is indicative for pronounced differences in bonding. These findings imply that the bonding mechanism in crystalline phase change materials differs substantially from conventional bonding mechanisms such as metallic, ionic, and covalent bonding. Instead, the data reported here confirm a recently developed conjecture, namely that metavalent bonding is a novel bonding mechanism besides those mentioned previously.
Highly Elastic and Ultratough Hybrid Ionic–Covalent Hydrogels with Tunable Structures and Mechanics
Authors: Yang Yanyu , Wang Xing , Yang Fei , Wang Luning , Wu Decheng
Published: March 2018

Hybrid ionically–covalently crosslinked double‐network (DN) hydrogels are attracting increasing attention on account of their self‐recovery ability and fatigue resistance, but their relative low mechanical strength and tedious performance adjustment severely limit their applications. Herein, a new strategy to concurrently fabricate hybrid ionic–covalent DN hydrogels and modulate their structures and mechanics is reported, in which an in situ formed chitosan ionic network is incorporated by post‐crosslinking the chitosan‐based composite hydrogel using multivalent anions solutions. The obtained hybrid DN hydrogels exhibit predominant mechanical properties including superior elastic modulus, high tensile strength, and ultrahigh fracture energy because of the more efficient energy dissipation of rigid short‐chain chitosan network. Notably, the swollen hydrogels still remain mechanically strong and tough even after immersion in water for 24 h. More significantly, simply changing the post‐crosslinking time can vary the compactness and rigidity of the chitosan network in situ, achieving flexible and efficient modulation of the structures and mechanics of the hybrid DN hydrogels. This study opens up a new horizon in the preparation and regulation of DN hydrogels for promising applications in tissue scaffolds, actuators, and wearable devices.
Highly Luminescent Lead Halide Perovskite Quantum Dots in Hierarchical CaF2 Matrices with Enhanced Stability as Phosphors for White Light‐Emitting Diodes
Authors: Wei Yi , Xiao Hui , Xie Zhongxi , Liang Shuang , Liang Sisi , Cai Xuechao , Huang Shanshan , Al Kheraif Abdulaziz A. , Jang Ho Seong , Cheng Ziyong , Lin Jun
Published: March 2018

Lead halide perovskite quantum dots (PQDs) have been widely recognized as highly luminescent materials for efficient optoelectronic applications owing to their fascinating electronic and optical properties. In spite of the excellent performances for the fabrication of lighting devices, the poor chemical instability greatly hampers their practical applications. The inevitable ion exchange and degradation driven from light, moisture, heat, and others limits their applications such as solid‐state light‐emitting diodes (LEDs). In this paper, the stability of PQDs is improved by integrating them in CaF2 hierarchical nanospheres (HNSs). In comparison with the pristine perovskite materials, the outstanding optical performances are well preserved. The perovskite displays a unique quantum confinement effect in the HNSs. Additionally, embedding the quantum dots in robust CaF2 matrices protects them from being damaged by moisture or light irradiation as well as anion exchange. Furthermore, white LED devices are obtained by mixing green CaF2‐CsPbBr3 composites and commercial red phosphors on a blue chip. The optimized devices show a high luminous efficacy of 62.7 lm W–1 under 20 mA current and preserve the value of 56.3 lm W–1 after working for 8 h.
Microstructures Fabricated by Two‐Photon Polymerization and Their Remote Manipulation Techniques: Toward 3D Printing of Micromachines
Authors: Lin Yang , Xu Jie
Published: March 2018

As a promising microfabrication method, two‐photon polymerization (TPP) underwent a rapid development for various applications in chemistry, biology, pharmaceuticals, microfluidics, and so forth. In recent years, the method has received particular attention because of its application for micromachines, including those requiring remote manipulation. Different manipulating techniques such as magnetic, optic, and acoustic manipulation are realized on TPP‐fabricated microstructures, demonstrating the great potential for further development of micromachines. Nonetheless, most of the work is still at early stages, only proofing conceptual ideas. For instance, magnetically driven microswimmers are only investigated in artificial experimental environments, and it is still challenging to tackle complex in vivo conditions. Although a long journey is still ahead for using these micromachines in daily life, it is predictable that the combination of two‐photon polymerization associated with remotely driven techniques will benefit various fields.
Photorefractive Effect in Organic–Inorganic Hybrid Perovskites and Its Application to Optical Phase Shifter
Authors: Tahara Hirokazu , Aharen Tomoko , Wakamiya Atsushi , Kanemitsu Yoshihiko
Published: March 2018

Single crystals of methylammonium lead trihalide perovskites with high optical transparency and well‐defined facets are grown via solution process. Using these high‐quality crystals, the photocarrier‐induced refractive‐index change is observed for the first time in organic–inorganic hybrid perovskites. The photorefractive properties are measured using a laser interferometric technique that enables to monitor the time‐resolved refractive phase shifts. It is found that these phase shifts are determined by the initial density of photogenerated carriers and they are surprisingly retained even after carrier recombination. Utilizing the extremely long‐lived phase shift, it is demonstrated that the perovskite single crystal works as a phase shifter of laser light to generate any desired polarization. Furthermore, a periodic polarization‐modulation technique is established using the time‐dependent refractive phase shift. This refractive property can be used for advanced optical applications of organic–inorganic hybrid perovskites.
Transition‐Metal‐Free Synthesis of Acridones via Base‐Mediated Intramolecular Oxidative C−H Amination
Authors: Wei Wen‐Tao , Sheng Jian‐Fei , Miao Hui , Luo Xiang , Song Xian‐Heng , Yan Ming , Zou Yong
Published: March 2018

Intramolecular oxidative C−H amination of 2‐aminobenzophenones was achieved in the presence of potassium tert‐butoxide and dimethyl sulfoxide. A series of functionalized acridones were prepared in moderate to excellent yields in a mild, efficient, and transition‐metal‐free manner.

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Direct Allylation of Active Methylene Compounds with Allylic Alcohols by Use of Palladium/Phosphine‐Borane Catalyst System
Authors: Shimizu Aika , Hirata Goki , Onodera Gen , Kimura Masanari
Published: March 2018

The C−C bond formation between active methylene compounds and allylic alcohols has been newly developed by using a palladium complex as a catalyst together with a phosphine‐borane ligand. The best phosphine‐borane ligand for this direct allylation has been revealed to be Ph2P(CH2)4(9‐BBN) to produce a variety of desirable allylated products in high yields.

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Recent Advances in the Construction of C–N Bonds Through Coupling Reactions between Carbon Radicals and Nitrogen Radicals
Authors: Luo Junfei , Wei Wen‐Ting
Published: March 2018

C−N bonds are widely found in natural products, medicinal molecules and multifunctional materials. In recent years, the construction of C−N bonds through a radical coupling reaction between carbon‐centered radicals with nitrogen‐centered radicals has emerged as a frontier area in organic chemistry. This review summarizes the recent advances (especially those after 2012) in radical coupling reactions that facilitate the formation of C−N bonds. The main achievements on this area are presented according to the pattern of the nitrogen‐centered radicals generated. Selected examples of substrates are listed and special attention is paid to the reaction mechanisms. Moreover, a personal outlook is described at the end.

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Molybdenum‐Catalyzed Sustainable Friedländer Synthesis of Quinolines
Authors: Rubio‐Presa Rubén , Suárez‐Pantiga Samuel , Pedrosa María R. , Sanz Roberto
Published: March 2018

Polysubstituted quinolines have been efficiently synthesized from nitroarenes and glycols, as reducing agents, under dioxomolybdenum(VI)‐catalysis. Interestingly, the waste reduction byproduct is incorporated into the final heterocycle. This method represents an efficient and sustainable variant of the Friedländer synthesis of quinolines.

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Multicolor T‐Ray Imaging Using Multispectral Metamaterials
Authors: Zhou Zhitao , Zhou Tao , Zhang Shaoqing , Shi Zhifeng , Chen Ying , Wan Wenjian , Li Xinxin , Chen Xinzhong , Gilbert Corder Stephanie N. , Fu Zhanglong , Chen Liang , Mao Ying , Cao Juncheng , Omenetto Fiorenzo G. , Liu Mengkun , Li Hua , Tao Tiger H.
Published: March 2018

Recent progress in ultrafast spectroscopy and semiconductor technology is enabling unique applications in screening, detection, and diagnostics in the Terahertz (T‐ray) regime. The promise of efficaciously operation in this spectral region is tempered by the lack of devices that can spectrally analyze samples at sufficient temporal and spatial resolution. Real‐time, multispectral T‐ray (Mul‐T) imaging is reported by designing and demonstrating hyperspectral metamaterial focal plane array (MM‐FPA) interfaces allowing multiband (and individually tunable) responses without compromising on the pixel size. These MM‐FPAs are fully compatible with existing microfabrication technologies and have low noise when operating in the ambient environment. When tested with a set of frequency switchable quantum cascade lasers (QCLs) for multicolor illumination, both MM‐FPAs and QCLs can be tuned to operate at multiple discrete THz frequencies to match analyte “fingerprints.” Versatile imaging capabilities are presented, including unambiguous identification of concealed substances with intrinsic and/or human‐engineered THz characteristics as well as effective diagnosis of cancerous tissues without notable spectral signatures in the THz range, underscoring the utility of applying multispectral approaches in this compelling wavelength range for sensing/identification and medical imaging.
A Monolithically Processed Rectifying Pixel for High‐Resolution Organic Imagers
Authors: Zalar Peter , Matsuhisa Naoji , Suzuki Toshiki , Enomoto Shintaro , Koizumi Mari , Yokota Tomoyuki , Sekino Masaki , Someya Takao
Published: March 2018

Integration of switching elements with sensing elements in a sensor array is a crucial platform for “sensing surfaces”. Of particular interest are imaging surfaces, especially for applications such as X‐ray imaging or fingerprint sensors. Since a photodiode loses its rectifying properties upon illumination, it requires a switching element so that meaningful data can be obtained from each individual pixel. To solve this problem, we have developed a monolithically processed rectifying pixel which enables high resolution organic imaging devices. Our organic imager has pixel pitches as small as 50 µm, with resolutions of up to 262 ppi. The pixel's individual light intensity dependent and spectral response characteristics were characterized as a function of voltage. As a total imaging system, the imageable resolution was also determined. The applicability of the imager was validated by steady state images, but also by real‐time video acquisition and by spatial photoplethysmography (PPG) measurements on the ball of a human foot.
A Review on the Features and Progress of Dual‐Ion Batteries
Authors: Wang Meng , Tang Yongbing
Published: March 2018

Despite the wide application of lithium‐ion batteries in portable electronic devices and electric vehicles, the demand for new battery systems with the merits of high voltage, environmental friendliness, safety, and cost efficiency is still quite urgent. This perspective focuses on dual‐ion batteries (DIBs), in which, both the cations and anions are involved in the battery reaction. An anion's intercalation/deintercalation process on the cathode side allows the DIBs to operate at high voltages, which is favorable for enhanced energy density. However, electrolytes with a wide electrochemical window and suitable anion‐intercalation materials with highly reversible capacities should be developed. The progress of research into stable organic electrolytes, ionic liquids, and their effects on the electrochemical performances of DIBs are first discussed. Thereafter, the anion‐host materials including graphitic materials, organic materials, and their working mechanisms are discussed in detail. In addition, recently emerging DIB systems with high‐capacity anodes, or sodium‐, potassium‐ion involved battery reactions are also reviewed. The authors' recent work, demonstrating a generalized DIB construction using metal foil as both current collector and alloying anode material, which is successfully extended into lithium‐, sodium‐, and potassium‐based DIBs, is also discussed.
Dendrite‐Free Metallic Lithium in Lithiophilic Carbonized Metal–Organic Frameworks
Authors: Zhu Mengqi , Li Bin , Li Songmei , Du Zhiguo , Gong Yongji , Yang Shubin
Published: March 2018

Although metallic lithium is a promising anode material due to its high theoretical capacity, the uncontrollable growth of lithium dendrites and infinite volume change hamper its practical applications. Here, the lithiophilic property of carbonized metal–organic frameworks (cMOFs) is harnessed with zinc species to achieve a uniform lithium‐cMOFs (Li‐cMOFs) hybrid via a molten lithium infusion approach. In the resultant Li‐cMOFs, not only are abundant Zn clusters are uniformly confined and dispersed in the matrix, serving as homogeneous nucleation sites to guide Li deposition, but also the 3D conductive porous structure enables the homogenization of the distributions of electric field and Li ion flux, avoiding the formation of lithium dendrites. Hence, this hybrid exhibits superior electrochemical performance with a very low voltage hysteresis and a good cycle life. This provides a new manner to achieve a series of stable metallic lithium anodes based on the large family of metal–organic frameworks with tunable metal species.
High‐Performance Suspended Particle Devices Based on Copper‐Reduced Graphene Oxide Core–Shell Nanowire Electrodes
Authors: Huang Shengyun , Zhang Qingzhe , Li Pandeng , Ren Fuqiang , Yurtsever Aycan , Ma Dongling
Published: March 2018

Smart windows are one of the key components of so‐called “green” buildings. These windows are based on an actively switchable electro‐optic material that is sandwiched between two transparent electrodes. Although great progress has been made in identifying the optimal materials for such active windows, there is still a great need to improve their key elements, especially the performance of the transparent electrodes. Here, a new suspended particle device (SPD), holding a great potential for smart window applications, which is built upon copper‐reduced graphene oxide (Cu‐rGO) core–shell nanowire (NW) films as a transparent conductive electrode is reported. With the wrapping of rGO, the Cu NW electrodes demonstrate both high optical transparency and electrical conductivity, as well as significantly improved stability under various testing conditions. The novel sandwich‐structured SPDs, based on these electrodes, show a large change in their optical transmittance (42%) between “on” and “off” states, impressively fast switching time and superior stability. These high performances are comparable to those of the SPDs based on indium tin oxide electrodes. These promising results pave the way for the electrodes to be an integral part of a variety of optoelectronic devices, including energy‐friendly and flexible electronics.
Toward the Experimental Understanding of the Energy Storage Mechanism and Ion Dynamics in Ionic Liquid Based Supercapacitors
Authors: Yan Runyu , Antonietti Markus , Oschatz Martin
Published: March 2018

A series of salt‐templated carbons with gradually changed pore structure and their corresponding nitrogen‐doped analogues are synthesized and applied as model systems to thoroughly study the ion migration dynamics and energy storage mechanism in hierarchical pore structures with different surface functionalization in electric double‐layer capacitors with a model ionic liquid electrolyte (1‐ethyl‐3‐methylimidazolium tetrafluoroborate). Ion conformation and phase variation during the charging/discharging process and their contribution to the energy storage mechanism are investigated. A significant contribution of structural changes in the bulk of the ionic liquid electrolyte strengthening charge storage in the electric double‐layer beyond the usual expectations is uncovered. Furthermore, a quantitative model of the structure–dynamics relationship is proposed, in which the optimal ratio of mesopores to micropores is determined to be 3:1 in pore volume. Below this ratio, the ion dynamics can be promoted by increasing mesopore content and/or doping with nitrogen, while those parameters show only minor influence when the ratio is surpassing 3:1. Nitrogen doping in this system improves the rate capability (due to the enhanced ion transport dynamics) rather than the amount of energy stored.
An Open‐Structured Matrix as Oxygen Cathode with High Catalytic Activity and Large Li2O2 Accommodations for Lithium–Oxygen Batteries
Authors: Lin Xiaodong , Yuan Ruming , Cai Senrong , Jiang Youhong , Lei Jie , Liu San‐Gui , Wu Qi‐Hui , Liao Hong‐Gang , Zheng Mingsen , Dong Quanfeng
Published: March 2018

The nonaqueous lithium–oxygen (Li–O2) battery is considered as one of the most promising candidates for next‐generation energy storage systems because of its very high theoretical energy density. However, its development is severely hindered by large overpotential and limited capacity, far less than theory, caused by sluggish oxygen redox kinetics, pore clogging by solid Li2O2 deposition, inferior Li2O2/cathode contact interface, and difficult oxygen transport. Herein, an open‐structured Co9S8 matrix with sisal morphology is reported for the first time as an oxygen cathode for Li–O2 batteries, in which the catalyzing for oxygen redox, good Li2O2/cathode contact interface, favorable oxygen evolution, and a promising Li2O2 storage matrix are successfully achieved simultaneously, leading to a significant improvement in the electrochemical performance of Li–O2 batteries. The intrinsic oxygen‐affinity revealed by density functional theory calculations and superior bifunctional catalytic properties of Co9S8 electrode are found to play an important role in the remarkable enhancement in specific capacity and round‐trip efficiency for Li–O2 batteries. As expected, the Co9S8 electrode can deliver a high discharge capacity of ≈6875 mA h g−1 at 50 mA g−1 and exhibit a low overpotential of 0.57 V under a cutoff capacity of 1000 mA h g−1, outperforming most of the current metal‐oxide‐based cathodes.
Comprehensive analysis on 559 cases of adrenal incidentalomas in the elderly Chinese
Authors: Li Tuo , Li Weiqin , Fang Xiao , Lv Qian , Song Yan , Shi Yongquan
Published: March 2018

Objective

This study was conducted to describe the incidence, classifications and characteristics of adrenal incidentalomas (AIs) in the elderly Chinese.

Methods

Primary clinical records in Shanghai Changzheng Hospital (n = 559) were collected for incident cases of AI between January 1, 2002 and December 1, 2016. We examined demographics, endocrine functions, treatment, etiology, and prognoses.

Results

We identified 559 new diagnoses of elderly onset AIs, of which 41.25% were male and were diagnosed at a mean age of 74.39 ± 9.03 years. About 61% showed no typical symptoms. Upon systematic review, 41.34% showed dysglycemia, high blood pressure, kaliopenia, and so on. 24.15% (n = 135) received complete or partial endocrine function assessments. A total of 281 cases underwent surgical treatment, and 278 cases went through regular follow‐ups without any operation. Preoperative evaluation was basically consistent with postoperative pathology (P > .05). During the follow‐up, the presence of new subclinical hypercortisolism was 8.99%, and the tumor grew up 3.92% per year (1.96 ± 0.09 mm). 51 cases (9.12%) eventually received further invasive examinations or surgical treatments.

Conclusion

The detection of AI in the elderly Chinese is increasing annually. The imaging method and endocrine function tests have great roles in distinguishing between benignancy and malignancy. The diagnosis and treatment of the elderly Chinese with AI should receive multidisciplinary assessment. Biochemical and morphological follow‐up of aged patients with AI should be conducted every 5 years at least.
Near‐UV activated, photostable nanophosphors for in vitro dosimetry and dynamic bioimaging
Authors: Spyrogianni Anastasia , Tiefenboeck Peter , Starsich Fabian H. L. , Keevend Kerda , Krumeich Frank , Herrmann Inge K. , Leroux Jean‐Christophe , Sotiriou Georgios A.
Published: March 2018

Luminescent rare earth nanoparticles exhibit superior optical stability over commonly‐used organic dyes and higher biocompatibility over quantum dots, rendering them advantageous as bioimaging nanoprobes. However, their typical excitation inhibits their broad employment with conventional fluorescence microscopes and, thus, solutions are sought to shift their activation in the long‐wavelength (near‐UV) spectral region. Here, we synthesize YVO4:Eu3+ nanophosphors by flame aerosol technology to systematically study the effect of Bi3+ codoping on their luminescence. That way, we identify an optimal Bi‐content for sufficient near‐UV activation. These nanophosphors are highly crystalline and appeared bright red under a conventional fluorescence microscope, facilitating bioimaging with HeLa cells and in vitro dosimetry correlations in the presence and absence of serum. The nanophosphor superiority over organic‐dye‐labeled silica nanoparticles is shown during dynamic imaging for 4 h without photobleaching for the former. These YVO4:Eu3+/Bi3+ nanophosphors can provide a non‐photobleaching tool for further dynamic nanoparticle‐cell interaction studies with conventional fluorescence microscopes. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2947–2957, 2018
Economic model predictive control of stochastic nonlinear systems
Authors: Wu Zhe , Zhang Junfeng , Zhang Zhihao , Albalawi Fahad , Durand Helen , Mahmood Maaz , Mhaskar Prashant , Christofides Panagiotis D.
Published: March 2018

This work focuses on the design of stochastic Lyapunov‐based economic model predictive control (SLEMPC) systems for a broad class of stochastic nonlinear systems with input constraints. Under the assumption of stabilizability of the origin of the stochastic nonlinear system via a stochastic Lyapunov‐based control law, an economic model predictive controller is proposed that utilizes suitable constraints based on the stochastic Lyapunov‐based controller to ensure economic optimality, feasibility and stability in probability in a well‐characterized region of the state‐space surrounding the origin. A chemical process example is used to illustrate the application of the approach and demonstrate its economic benefits with respect to an EMPC scheme that treats the disturbances in a deterministic, bounded manner. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3312–3322, 2018
Inferring the evolutionary reduction of corm lobation in Isoëtes using Bayesian model‐averaged ancestral state reconstruction
Authors: Freund Forrest D. , Freyman William A. , Rothfels Carl J.
Published: March 2018

Premise of the Study

Inferring the evolution of characters in Isoëtes has been problematic, as these plants are morphologically conservative and yet highly variable and homoplasious within that conserved base morphology. However, molecular phylogenies have given us a valuable tool for testing hypotheses of character evolution within the genus, such as the hypothesis of ongoing morphological reductions.

Methods

We examined the reduction in lobe number on the underground trunk, or corm, by combining the most recent molecular phylogeny with morphological descriptions gathered from the literature and observations of living specimens. Ancestral character states were inferred using nonstationary evolutionary models, reversible‐jump MCMC, and Bayesian model averaging.

Key Results

Our results support the hypothesis of a directional reduction in lobe number in Isoëtes, with the best‐supported model of character evolution being one of irreversible reduction. Furthermore, the most probable ancestral corm lobe number of extant Isoëtes is three, and a reduction to two lobes has occurred at least six times.

Conclusions

From our results, we can infer that corm lobation, like many other traits in Isoëtes, shows a degree of homoplasy, and yet also shows ongoing evolutionary reduction.
Is age of menarche among school girls related to breastfeeding during infancy?
Authors: Al‐Mathkoori Radhia , Albatineh Ahmed , Al‐Shatti Maryam , Al‐Taiar Abdullah
Published: March 2018

Objectives

Breastfeeding has been linked to various disease conditions in adulthood. Age of menarche has been proposed to be an intermediary factor on the life‐course path to these disease conditions, but the link between breastfeeding and age of menarche remains under debate. This study aimed to investigate the association between age of menarche and breastfeeding during infancy.

Methods

A cross‐sectional study was conducted in which 775 female high school students were randomly selected from private and public high schools in all provinces in Kuwait. Data on age of menarche were collected by self‐administered questionnaires from the students, while data on breastfeeding were collected from their mothers through telephone interviews. Multiple linear regression was used to investigate the association between breastfeeding and age of menarche after adjusting for potential confounders.

Results

Of the study group 496 mothers responded to the telephone interview. Duration of breastfeeding was not significantly associated with age of menarche before or after adjusting for potential confounders (P = .279 and P = .124 for crude and fully adjusted model, respectively). Similarly, no significant association was found between type of breastfeeding during the first four months of life and age of menarche before or after adjusting for potential confounders (P = .949 and P = .398 for crude and fully adjusted model, respectively).

Conclusion

No significant association was found between age of menarche and breastfeeding during infancy, which may suggest that the link between breastfeeding and disease conditions in adulthood is not necessarily mediated through age of menarche.
Asbestos standards: Impact of currently uncounted chrysotile asbestos fibers on lifetime lung cancer risk
Authors: Richardson David B. , Keil Alexander P. , Cole Stephen R. , Dement John
Published: March 2018

Background

Current regulations require that asbestos fibers are collected and examined using a light microscope. This method fails to enumerate fibers that are too short or thin to reliably count using a light microscope under normal conditions.

Methods

A cohort of 3054 workers employed at an asbestos textile plant was followed to ascertain causes of death. Exposure was almost entirely chrysotile. Fiber counts were quantified using light microscopy and electron microscopy. The g‐formula was used to estimate impacts on lung cancer of policies defined in terms of fiber counts quantified using light and electron microscopy.

Results

Given exposure at the current standard, the estimated lung cancer risk was 7.33%, comparable to the risk expected under a standard of 1 fiber/mL counted using electron microscopy (7.30%). The lifetime risk of lung cancer under a standard of 0.1 fiber/mL counted by electron microscopy was estimated to be 7.10%.

Conclusions

We identify policies defined in terms of electron microscopy‐based asbestos exposure metrics that yield comparable, or lower, lung cancer mortality than that expected under the current standard.
Recent Progress in Transition‐Metal‐Free, Base‐Mediated Benzannulation Reactions for the Synthesis of a Diverse Range of Aromatic and Heteroaromatic Compounds
Authors: Poudel Tej Narayan , Tamargo Ramuel John Inductivo , Cai Hongyun , Lee Yong Rok
Published: March 2018

Benzene and its derivatives are the most abundant substructures of several interesting classes of compound, such as bioactive molecules. Owing to their importance, the development of methods for their construction has attracted considerable attention. However, the regioselective synthesis of polysubstituted aromatic and heteroaromatic compounds by using aromatic substitution is challenging, because it provides derivatives with restricted substitution patterns. Therefore, the benzannulation reaction—the assembly of benzene derivatives from acyclic precursors—constitutes a superior and highly versatile approach to polysubstituted aromatic and heteroaromatic compounds, and various efficient benzannulation reactions have been reported. Representative examples include Cs2CO3, t‐BuOK, and DBU‐catalyzed reactions for the construction of valuable benzene derivatives. The central objective of this Focus Review is to highlight base‐mediated benzannulation reactions under transition‐metal‐free conditions for the construction of aromatic and heteroaromatic compounds.
Neutron‐based computed microtomography: Pliobates cataloniae and Barberapithecus huerzeleri as a test‐case study
Authors: Urciuoli Alessandro , Zanolli Clément , Fortuny Josep , Almécija Sergio , Schillinger Burkhard , Moyà‐Solà Salvador , Alba David M.
Published: March 2018

Objectives

High‐resolution imaging of fossils with X‐ray computed microtomography (μCT) has become a very powerful tool in paleontological research. However, fossilized bone, embedding matrix, and dental tissues do not always provide a distinct structural signal with X‐rays. We demonstrate the benefits of high‐resolution neutron radiation in three different specimens showing problematic contrasts with X‐ray μCT.

Materials and methods

We compare neutron with X‐ray μCT scans of fossils from two Miocene catarrhines from the Vallès‐Penedès Basin: the cranium (IPS58443.1, holotype) of the putative stem hominoid Pliobates cataloniae, to discriminate between bone and matrix; and two lower molars (IPS1724n,o, holotype) of Barberapithecus huerzeleri, to discriminate among dental tissues.

Results

X‐ray μCT scans of these specimens fail to retrieve any contrast between matrix/bone and enamel/dentine, whereas neutron μCT scans deliver high‐contrast images, enabling a proper evaluation of the specimens' internal anatomy.

Discussion

Low bone/matrix intensity difference with X‐ray μCT scans in IPS58443.1 is due to the extreme similarity in chemical composition between the matrix and the fossilized tissues, and the presence of high‐density elements. In IPS1724, it is attributable to the convergence of enamel and dentine compositions during fossilization. On the contrary, neutron radiation returns very different contrasts for different isotopes of the same element and easily penetrates most metals. Neutron‐based μCT scans therefore enable a correct definition of the bone/sediment and enamel/dentine interfaces, and hence a better segmentation of the images stack. We conclude that neutron radiation represents a successful alternative for high‐resolution µCT of small‐sized fossils that are problematic with X‐rays.
Status epilepticus: Role for etiology in determining response to benzodiazepines
Authors: Joshi Suchitra , Rajasekaran Karthik , Hawk Kyle M. , Chester Stephen J. , Goodkin Howard P.
Published: March 2018

Objective

Clinical factors contributing to benzodiazepine failure in treating status epilepticus (SE) include suboptimal dosing and seizure duration. As many benzodiazepine‐refractory episodes of SE arise from acute etiologies, we sought to determine whether etiology impacts SE treatment.

Methods

The potency of diazepam to terminate SE induced by lithium‐pilocarpine (LiPilo‐SE) or kainic acid (KA‐SE) in 3‐week‐old rats was studied by video‐electroencephalography. Synaptic γ‐aminobutyric acid type A receptor (GABAR)‐mediated currents were recorded from dentate granule cells using voltage‐clamp electrophysiology. Surface expression of γ2 subunit–containing GABARs and Kv4.2 potassium channels in hippocampal slices was determined using a biotinylation assay. Expression of phosphorylated forms of β2/3 and γ2 subunits was determined using phosphospecific antibodies and Western blotting.

Results

Diazepam failed to terminate late SE in LiPilo‐SE animals but was successful in terminating KA‐SE of 1‐ and 3‐hour duration. One hour after SE onset, GABAR‐mediated synaptic inhibition and γ2 subunit–containing GABAR surface expression were reduced in LiPilo‐SE animals. These were unchanged in KA‐SE animals at 1 and 3 hours. Phosphorylation of γ2 subunit residue S327 was unchanged in both models, although GABAR β3 subunit S408/409 residues were dephosphorylated in the LiPilo‐SE animals. Kv4.2 potassium channel surface expression was increased in LiPilo‐SE animals but reduced in KA‐SE animals.

Interpretation

SE‐model–dependent differences support a novel hypothesis that the development of benzodiazepine pharmacoresistance may be etiologically predetermined. Further studies are required to investigate the mechanisms that underlie such etiological differences during SE and whether etiology‐dependent protocols for the treatment of SE need to be developed. Ann Neurol 2018;83:830–841
Regional brain volumetry and brain function in severely brain‐injured patients
Authors: Annen Jitka , Frasso Gianluca , Crone Julia Sophia , Heine Lizette , Di Perri Carol , Martial Charlotte , Cassol Helena , Demertzi Athena , Naccache Lionel , Laureys Steven ,   and Coma Science Group Collaborators
Published: March 2018

Objective

The relationship between residual brain tissue in patients with disorders of consciousness (DOC) and the clinical condition is unclear. This observational study aimed to quantify gray (GM) and white matter (WM) atrophy in states of (altered) consciousness.

Methods

Structural T1‐weighted magnetic resonance images were processed for 102 severely brain‐injured and 52 healthy subjects. Regional brain volume was quantified for 158 (sub)cortical regions using Freesurfer. The relationship between regional brain volume and clinical characteristics of patients with DOC and conscious brain‐injured patients was assessed using a linear mixed‐effects model. Classification of patients with unresponsive wakefulness syndrome (UWS) and minimally conscious state (MCS) using regional volumetric information was performed and compared to classification using cerebral glucose uptake from fluorodeoxyglucose positron emission tomography. For validation, the T1‐based classifier was tested on independent datasets.

Results

Patients were characterized by smaller regional brain volumes than healthy subjects. Atrophy occurred faster in UWS compared to MCS (GM) and conscious (GM and WM) patients. Classification was successful (misclassification with leave‐one‐out cross‐validation between 2% and 13%) and generalized to the independent data set with an area under the receiver operator curve of 79% (95% confidence interval [CI; 67–91.5]) for GM and 70% (95% CI [55.6–85.4]) for WM.

Interpretation

Brain volumetry at the single‐subject level reveals that regions in the default mode network and subcortical gray matter regions, as well as white matter regions involved in long range connectivity, are most important to distinguish levels of consciousness. Our findings suggest that changes of brain structure provide information in addition to the assessment of functional neuroimaging and thus should be evaluated as well. Ann Neurol 2018;83:842–853
Genetic predisposition in anti‐LGI1 and anti‐NMDA receptor encephalitis
Authors: Mueller Stefanie H. , Färber Anna , Prüss Harald , Melzer Nico , Golombeck Kristin S. , Kümpfel Tania , Thaler Franziska , Elisak Martin , Lewerenz Jan , Kaufmann Max , Sühs Kurt‐Wolfram , Ringelstein Marius , Kellinghaus Christoph , Bien Christian G. , Kraft Andrea , Zettl Uwe K. , Ehrlich Sven , Handreka Robert , Rostásy Kevin , Then Bergh Florian , Faiss Jürgen H. , Lieb Wolfgang , Franke Andre , Kuhlenbäumer Gregor , Wandinger Klaus‐Peter , Leypoldt Frank ,   on behalf of the German Network for Research on Autoimmune Encephalitis (GENERATE)
Published: March 2018

We performed a genome‐wide association study in 1,194 controls and 150 patients with anti‐N‐methyl‐D‐aspartate receptor (anti‐NMDAR, n = 96) or anti‐leucine‐rich glioma‐inactivated1 (anti‐LGI1, n = 54) autoimmune encephalitis. Anti‐LGI1 encephalitis was highly associated with 27 single‐nucleotide polymorphisms (SNPs) in the HLA‐II region (leading SNP rs2858870 p = 1.22 × 10−17, OR = 13.66 [7.50–24.87]). Potential associations, below genome‐wide significance, were found with rs72961463 close to the doublecortin‐like kinase 2 gene (DCLK2) and rs62110161 in a cluster of zinc‐finger genes. HLA allele imputation identified association of anti‐LGI1 encephalitis with HLA‐II haplotypes encompassing DRB1*07:01, DQA1*02:01 and DQB1*02:02 (p < 2.2 × 10−16) and anti‐NMDAR encephalitis with HLA‐I allele B*07:02 (p = 0.039). No shared genetic risk factors between encephalitides were identified. Ann Neurol 2018;83:863–869
Developmental conduction aphasia after neonatal stroke
Authors: Northam Gemma B. , Adler Sophie , Eschmann Kathrin C. J. , Chong Wui K. , Cowan Frances M. , Baldeweg Torsten
Published: March 2018

Objective

Impairment of speech repetition following injury to the dorsal language stream is a feature of conduction aphasia, a well‐described “disconnection syndrome” in adults. The impact of similar lesions sustained in infancy has not been established.

Methods

We compared language outcomes in term‐born individuals with confirmed neonatal stroke (n = 30, age = 7–18 years, left‐sided lesions in 21 cases) to matched controls (n = 40). Injury to the dorsal and/or ventral language streams was assessed using T1‐ and T2‐weighted magnetic resonance imaging (MRI) and diffusion tractography. Language lateralization was determined using functional MRI.

Results

At the group level, left dorsal language stream injury was associated with selective speech repetition impairment for nonwords (p = 0.021) and sentences (p < 0.0001). The majority of children with significant repetition impairment had retained left hemisphere language representation, but right hemisphere dominance was correlated with minimal or absent repetition deficits. Post hoc analysis of the repetition‐impaired group revealed additional language‐associated deficits, but these were more subtle and variable.

Interpretation

We conclude that (1) despite the considerable plasticity of the infant brain, early dorsal language stream injury can result in specific and long‐lasting problems with speech repetition that are similar to the syndrome of conduction aphasia seen in adults; and (2) language reorganization to the contralateral hemisphere has a protective effect. Ann Neurol 2018;83:664–675 Ann Neurol 2018;83:664–675
Elektronische Kommunikation zwischen zwei [10]Cycloparaphenylenen und Bisazafulleren (C59N)2 induziert durch kooperative Komplexierung
Authors: Rio Jérémy , Beeck Sebastian , Rotas Georgios , Ahles Sebastian , Jacquemin Denis , Tagmatarchis Nikos , Ewels Chris , Wegner Hermann A.
Published: March 2018

Ein Komplex aus [10]Cycloparaphenylen ([10]CPP) mit dem Bisazafulleren (C59N)2 wurde experimentell und computerchemisch untersucht. In dieser Struktur sind zwei [10]CPP‐Ringe an das dimere Azafulleren gebunden, [10]CPP⊃(C59N)2⊂[10]CPP. Die beobachteten photophysikalischen und Redox‐Eigenschaften lassen auf eine elektronische Interaktion zwischen den Komponenten schließen, insbesondere mit dem zweiten [10]CPP. Im Gegensatz zu [10]CPP⊃C60, in dem nur eine vernachlässigbare elektronische Kommunikation zwischen den Komponenten beobachtet wurde, konnte zwischen dem [10]CPP und dem (C59N)2 durch Lichtanregung ein Ladungstransferphänomen induziert werden, ähnlich einem mit einem CPP eingekapselten Metallofulleren. Solch elektronenreiche Fullerenspezies zeigen C60‐artige Grundzustandseigenschaften und verhalten sich im angeregten Zustand wie Metallofullerene. Diese Eigenschaft eröffnet neue Möglichkeiten für die Konstruktion von funktionalen supramolekularen Architekturen mit organischen Materialien.
Biokatalytische Oxidationsreaktionen – aus der Sicht eines Chemikers
Authors: Dong JiaJia , Fernández‐Fueyo Elena , Hollmann Frank , Paul Caroline E. , Pesic Milja , Schmidt Sandy , Wang Yonghua , Younes Sabry , Zhang Wuyuan
Published: March 2018

Enzyme gewinnen immer mehr Bedeutung als Katalysatoren für organische Oxidationsreaktionen. Mit Oxidoreduktasen stehen dem Chemiker vielseitige Werkzeuge für selektive und effiziente Oxidationsreaktionen zur Verfügung. Ihr Spektrum reicht von einfachen Alkoholoxidationen bis hin zur stereoselektiven Halogenierung nicht‐aktivierter C‐H‐Bindungen. Für viele biokatalytische Oxidationen ist bisher kein chemisches Pendant bekannt. Daher ermöglichen Oxidoreduktasen kürzere Syntheserouten. Darüber hinaus sind die generell milderen Reaktionsbedingungen biokatalytischer Oxidationen attraktiv. In diesem Aufsatz fassen wir einige aktuelle Entwicklungen im Bereich der biokatalytischen Oxidation zusammen. Wir beschreiben auch derzeitige Grenzen und vielversprechende Lösungsansätze.
Ein weiterer “unerhörter” Wieland‐Mechanismus bestätigt: Wasserstoffbildung aus Wasserstoffperoxid, Formaldehyd und Natriumhydroxid
Authors: Czochara Robert , Litwinienko Grzegorz , Korth Hans‐Gert , Ingold Keith U.
Published: March 2018

1923 berichteten Wieland und Wingler, dass an der Wasserstoff‐produzierenden Reaktion von Wasserstoffperoxid mit Formaldehyd in basischer Lösung keine freien Wasserstoffatome (H.) beteiligt sind. Sie postulierten als Zwischenstufe Bis(hydroxymethyl)peroxid (HOCH2OOCH2OH), das anschließend in H2 und Formiat zerfällt und schlugen einen Mechanismus vor, der heutzutage als “konzertierter Prozess” betrachtet würde. Seit dieser Zeit wurden verschiedene andere (widersprüchliche) “Mechanismen” vorgeschlagen. NMR‐ und Raman‐spektroskopische sowie kinetische Untersuchungen, speziell die Bestimmung des Deuterium‐kinetischen Isotopeneffekts (DKIE), belegen nun, dass in dieser basenabhängigen Reaktion beide H‐Atome im H2 von der CH2‐Gruppe des Formaldehyds stammen und nicht von den OH‐Gruppen von HOCH2OOCH2OH oder Wasser. Quantenchemische CBS‐QB3‐ und W1BD‐Rechnungen bestätigen, dass die H2‐Freisetzung über einen konzertierten Prozess verläuft, der durch doppelte Deprotonierung von HOCH2OOCH2OH stark beschleunigt wird. Ein Weg über freie Radikale kann ausgeschlossen werden.