bluuebunny/crossref_metadata_2025 huggingface dataset:
Prevalence and occupational covariates of mood, anxiety disorders, and alcohol dependence in a French ancillary staff population
Authors: Thiébaut R. , Martin C. , Grabot D. , Verdun-Esquer C. , Gabinski P. , Tignol J.
Published: July 2002

The aim of this study was to confirm the high prevalence of three frequent psychiatric disorders : anxiety, depressive illnesses, and alcohol dependence among ancillary staff, and to examine for occupational risk factors. Two hundred and forty-six women were randomly selected from the ancillary staff of the regional hospital centre of Bordeaux, and 186 subjects were interviewed between June 1996 and October 1997. First, a self-administrated questionnaire was completed concerning socio-economic status, lifestyle, health, and working conditions. Second, the two sections of the composite international diagnosis interview (CIDI), devoted to explore anxiety and depression, and the short Michigan alcoholism screening test (S-MAST) were used.

Mean age of the subjects was 40.8 years (SD = 8.3 years). During the year preceding the interview, 77 (42.5 %) subjects had stopped their job because of illness. Prevalence of the psychiatric disorders studied was 33.9 % (95 % confidence interval, 27.1-40.7 %). These disorders were related to sickness absence. This is why the use of drugs raises questions for work physicians. Two protective factors associated against depression in logistic regression analysis were found: training at the time of employment, and the task ‘cleaning sickroom’.

A high prevalence of psychiatric disorders was confirmed and occupational risk factors for the prevalence of increased psychiatric disorders were isolated that could have practical consequences, such as for the training at time of employment.
Knockdown of microglial Cav2.2 N‐type voltage‐dependent Ca2+ channel ameliorates behavioral deficits in a mouse model of Parkinson’s disease
Authors: Saegusa Hironao , Li Xu , Wang Xinshuang , Kayakiri Midori , Tanabe Tsutomu
Published: June 2020

Cav2.2 N‐type voltage‐dependent Ca2+ channel (VDCC) expressed in neurons is known to be essential for neurotransmitter release. We have shown previously that this channel is also expressed in nonexcitable microglia and plays pivotal roles in microglial functions. Here, we have examined the effects of microglia‐specific knockdown (KD) of Cav2.2 channel in a mouse model of Parkinson’s disease (PD). We found that the KD of Cav2.2 channel reduces the accumulation of microglia in the substantia nigra and ameliorates the behavioral deficits in PD model mice. These results are in marked contrast with those found in microglia‐specific KD of Cav1.2 L‐type channel, where exacerbated symptoms are observed. Our results suggest that blockade of microglial Cav2.2 N‐type VDCC is beneficial for the treatment of PD.
Luenberger‐typecubic observers for state estimation of linear systems
Authors: Share Pasand Mohammad Mahdi
Published: June 2020

This article introduces a new nonlinear observer for state estimation of linear time invariant systems. The proposed observer contains a (nonlinear) cubic term to enhance observer response. Unlike previously proposed observers, the cubic observer has nonlinear estimation error dynamics. Convergence criteria, performance advantages, and observer‐based feedback control with cubic observers are addressed. Simulation examples demonstrating performance improvement compared with linear observers, are included.
Liquid Biopsy Strategies to Distinguish Progression from Pseudoprogression and Radiation Necrosis in Glioblastomas
Authors: Yekula Anudeep , Muralidharan Koushik , Rosh Zachary S. , Youngkin Anna E. , Kang Keiko M. , Balaj Leonora , Carter Bob S.
Published: June 2020

Liquid biopsy for the detection and monitoring of central nervous system tumors is of significant clinical interest. At initial diagnosis, the majority of patients with central nervous system tumors undergo magnetic resonance imaging (MRI), followed by invasive brain biopsy to determine the molecular diagnosis of the WHO 2016 classification paradigm. Despite the importance of MRI for long‐term treatment monitoring, in the majority of patients who receive chemoradiation therapy for glioblastoma, it can be challenging to distinguish between radiation treatment effects including pseudoprogression, radiation necrosis, and recurrent/progressive disease based on imaging alone. Tissue biopsy‐based monitoring is high risk and not always feasible. However, distinguishing these entities is of critical importance for the management of patients and can significantly affect survival. Liquid biopsy strategies including circulating tumor cells, circulating free DNA, and extracellular vesicles have the potential to afford significant useful molecular information at both the stage of diagnosis and monitoring for these tumors. Here, current liquid biopsy‐based approaches in the context of tumor monitoring to differentiate progressive disease from pseudoprogression and radiation necrosis are reviewed.
Realizing the Intrinsic Electrochemical Activity of Acidic N‐Doped Graphene through 1‐Pyrenesulfonic Acid Bridges
Authors: Pan Meilan , Liu Subiao , Chew Jia Wei
Published: June 2020

Electrochemical technology attracts much research interest for the treatment of metal complexes, but most electrocatalysts are incapable of effectively degrading metal complexes, which generally have highly stable cages with five or six rings coordinating with metal ions. To address this, a bridging agent linking the catalysts and metal complexes can lower the energy barrier, and thus holds much promise to facilitate the removal of such pollutants. In this study, 1‐pyrenesulfonic acid (PSA) functionalization of acidic nitrogen‐doped graphene (ANG) is successfully synthesized and found to effectively remove metal complexes through electrochemical membrane filtration. Results indicate that PSA, interacting with Cu‐EDTA via the strong ion exchange of super acidic sulfonic (−SO3H) groups, acts as a conductive “bridge” connecting the electrocatalyst and metal complexes to overcome the challenge with penetrating the “cage” structure of metal complexes. The pyrrolic nitrogen of ANG is found to be the active sites in the electrochemical process, with the intrinsic electrochemical activity realized by the bridging agent, namely, PSA. This study highlights the importance of compounds with sulfonyl groups in circumventing the stable “cage” of the metal complexes, and thereby paves the way for effective degradation of such pollutants.
On the Largest Possible Mobility of Molecular Semiconductors and How to Achieve It
Authors: Nematiaram Tahereh , Padula Daniele , Landi Alessandro , Troisi Alessandro
Published: June 2020

A large database of known molecular semiconductors is used to define a plausible physical limit to the charge carrier mobility achievable within this materials class. From a detailed study of the desirable properties in a large dataset, it is possible to establish whether such properties can be optimized independently and what would be a reasonably achievable optimum for each of them. All relevant parameters are computed from a set of almost five thousand known molecular semiconductors, finding that the best known materials are not ideal with respect to all properties. These parameters in decreasing order of importance are the molecular area, the nonlocal electron–phonon coupling, the 2D nature of transport, the local electron–phonon coupling, and the highest transfer integral. It is also found that the key properties related to the charge transport are either uncorrelated or “constructively” correlated (i.e., they improve together) concluding that a tenfold increase in mobility is within reach in a statistical sense, on the basis of the available data. It is demonstrated that high throughput screenings, when coupled with physical models of transport produce both specific target materials and a more general physical understanding of the materials space.
Smart Oral Administration of Polydopamine‐Coated Nanodrugs for Efficient Attenuation of Radiation‐Induced Gastrointestinal Syndrome
Authors: Zhang Yushuo , Wang Lu , Xu Meiyun , Zhao Tongxin , Kuang Liangju , Hua Daoben
Published: June 2020

High‐dose ionizing radiation can lead to death from the unrecoverable damage of the gastrointestinal tract, especially the small intestine. Until now, the lack of predilection for the small intestine and rapid clearance by digestive fluids limit the effects of conventional radioprotective formulations. Herein, an innovative radioprotective strategy is developed for attenuating gastrointestinal syndrome by smart oral administration nanodrugs. The nanodrug is first engineered by encapsulating thalidomide into chitosan‐based nanoparticles, and then coated with polydopamine. The behaviors of gastric acid‐resistance, and pH‐switchable controlled release in the small intestine enhance the oral bioavailability of the pyroptosis inhibitor thalidomide. In a mouse model, nanodrugs demonstrate prolonged small intestinal residence time and accessibility to the crypt region deep in the mucus. Furthermore, the nanodrugs ameliorate survival rates of C57BL/6J mice irradiated by 14 Gy of subtotal body irradiation and also maintain their epithelial integrity. This work may provide a promising new approach for efficiently attenuating lethal radiation‐induced gastrointestinal syndrome and add insights into developing nanodrug‐based therapies with improved efficacy and minimum side effects.
Injectable Functional Biomaterials for Minimally Invasive Surgery
Authors: Raucci Maria Grazia , D'Amora Ugo , Ronca Alfredo , Ambrosio Luigi
Published: June 2020

Injectable materials represent very attractive ready‐to‐use biomaterials for application in minimally invasive surgical procedures. It is shown that this approach to treat, for example, vertebral fracture, craniofacial defects, or tumor resection has significant clinical potential in the biomedical field. In the last four decades, calcium phosphate cements have been widely used as injectable materials for orthopedic surgery due to their excellent properties in terms of biocompatibility and osteoconductivity. However, few clinical studies have demonstrated certain weaknesses of these cements, which include high viscosity, long degradation time, and difficulties being manipulated. To overcome these limitations, the use of sol‐gel technology has been investigated, which has shown good results for synthesis of injectable calcium phosphate‐based materials. In the last few decades, injectable hydrogels have gained increasing attention owing to their structural similarities with the extracellular matrix, easy process conditions, and potential applications in minimally invasive surgery. However, the need to protect cells during injection leads to the development of double network injectable hydrogels that are capable of being cross‐linked in situ. This review will provide the current state of the art and recent advances in the field of injectable biomaterials for minimally invasive surgery.
A Flexi‐PEGDA Upconversion Implant for Wireless Brain Photodynamic Therapy
Authors: Teh Daniel Boon Loong , Bansal Akshaya , Chai Chou , Toh Tan Boon , Tucker Robert Alan Jappy , Gammad Gil Gerald Lasam , Yeo Yanzhuang , Lei Zhendong , Zheng Xiang , Yang Fengyuan , Ho John S. , Bolem Nagarjun , Wu Bing Cheng , Gnanasammandhan Muthu Kumar , Hooi Lissa , Dawe Gavin Stewart , Libedinsky Camilo , Ong Wei‐Yi , Halliwell Barry , Chow Edward Kai‐Hua , Lim Kah‐Leong , Zhang Yong , Kennedy Brian K.
Published: June 2020

Near‐infrared (NIR) activatable upconversion nanoparticles (UCNPs) enable wireless‐based phototherapies by converting deep‐tissue‐penetrating NIR to visible light. UCNPs are therefore ideal as wireless transducers for photodynamic therapy (PDT) of deep‐sited tumors. However, the retention of unsequestered UCNPs in tissue with minimal options for removal limits their clinical translation. To address this shortcoming, biocompatible UCNPs implants are developed to deliver upconversion photonic properties in a flexible, optical guide design. To enhance its translatability, the UCNPs implant is constructed with an FDA‐approved poly(ethylene glycol) diacrylate (PEGDA) core clad with fluorinated ethylene propylene (FEP). The emission spectrum of the UCNPs implant can be tuned to overlap with the absorption spectra of the clinically relevant photosensitizer, 5‐aminolevulinic acid (5‐ALA). The UCNPs implant can wirelessly transmit upconverted visible light till 8 cm in length and in a bendable manner even when implanted underneath the skin or scalp. With this system, it is demonstrated that NIR‐based chronic PDT is achievable in an untethered and noninvasive manner in a mouse xenograft glioblastoma multiforme (GBM) model. It is postulated that such encapsulated UCNPs implants represent a translational shift for wireless deep‐tissue phototherapy by enabling sequestration of UCNPs without compromising wireless deep‐tissue light delivery.
A Zeolitic‐Imidazole Frameworks‐Derived Interconnected Macroporous Carbon Matrix for Efficient Oxygen Electrocatalysis in Rechargeable Zinc–Air Batteries
Authors: Douka Abdoulkader Ibro , Xu Yangyang , Yang Huan , Zaman Shahid , Yan Ya , Liu Hongfang , Salam Manzola Abdou , Xia Bao Yu
Published: June 2020

Nanostructures derived from zeolitic‐imidazole frameworks (ZIFs) gain much interest in bifunctional oxygen electrocatalysis. However, they are not satisfied well for long‐life rechargeable zinc–air batteries due to the limited single particle morphology. Herein, the preparation of an interconnected macroporous carbon matrix with a well‐defined 3D architecture by the pyrolysis of silica templated ZIF‐67 assemblies is reported. The matrix catalyst assembled zinc–air battery exhibits a high power density of 221.1 mW cm−2 as well as excellent stability during 500 discharging/charging cycles, surpassing that of a commercial Pt/C assembled battery. The synergistic effect from the interconnected macroporous structure together with abundant cobalt–nitrogen–carbon active sites justify the excellent electrocatalytic activity and battery performance. Considering the advanced nanostructures and performance, the as‐synthesized hybrid would be promising for rechargeable zinc–air batteries and other energy technologies. This work may also provide significant concept in the view of electrocatalysis design for long‐life battery.
Topological Surface State of Bi2Se3 Modified by Adsorption of Organic Donor Molecule Tetrathianaphthacene
Authors: Kitazawa Tatsuya , Yaji Koichiro , Shimozawa Kosuke , Kondo Hiroshi , Yamanaka Takayoshi , Yaguchi Hiroshi , Ishida Yukiaki , Kuroda Kenta , Harasawa Ayumi , Iwahashi Takashi , Ouchi Yukio , Komori Fumio , Shin Shik , Kanai Kaname
Published: June 2020

Topological insulators (TIs) are expected to realize new spintronic devices with low dissipative electrical transport. Organic molecule/TI interfaces have been investigated to explore the potential of multifunctional organic molecules for TI devices. However, there is no unified understanding of the interfacial electronic structure. The electronic structure of the molecular side must be examined to fully understand the phenomena at the interface. Thus, this paper reports the investigation of the interface between the electron‐donating organic molecule tetrathianaphthacene (TTN) and prototypical TI Bi2Se3 by ultraviolet photoemission spectroscopy (UPS), X‐ray photoemission spectroscopy (XPS), and angle‐resolved photoemission spectroscopy (ARPES). The deformation of the Fermi surface of the topological surface states as well as the formation of a 2D electron gas state (2DEG) at the interface occurs upon TTN deposition onto Bi2Se3. Confinement of the 2DEG into the surface arises from band‐bending accompanied by electron donation from TTNs to Bi2Se3 according to XPS and UPS. The knowledge obtained in this work shed new light on the understanding of the electronic structure of organic molecules/TI interfaces and open the door to the TI applications via modification by electronic functional organic molecules.
Flexible Electronic Systems on Plastic Substrates and Textiles for Smart Wearable Technologies
Authors: Baeg Kang‐Jun , Lee Jiyoul
Published: June 2020

The future era of hyperconnected information technology demands smart wearable devices, which provide ubiquitous human‐oriented service platforms and imperceptible computing with hands‐free and lightweight gadgets. Wearable devices have progressively developed from accessories such as glasses, wrist bands, and watches to embedded types in fibers or textiles, skin tattoos, and even implanted in the user's body. As a crucial component of smart applications, the flexible electronic system should contain embedded active electronic components such as transistors and integrated circuitry for processing data acquired in sensors and transmitting them to wireless communication systems. The substrates of these flexible electronic systems have also expanded from flexible plastic substrates to conformable ones such as fabrics and textiles. Here, recent progresses in flexible electronic systems, composed of transistor‐based circuitry and active matrix built on plastics or textile substrates, with an emphasis on fabrication using the conventional technology for electronic materials, are reviewed. In addition, emerging application areas of smart wearable technologies in a health monitoring system are also presented.
Effective Manipulation of Spin Dynamics by Polarization Electric Field in InGaN/GaN Quantum Wells at Room Temperature
Authors: Liu Xingchen , Tang Ning , Zhang Shixiong , Zhang Xiaoyue , Guan Hongming , Zhang Yunfan , Qian Xuan , Ji Yang , Ge Weikun , Shen Bo
Published: June 2020

III‐nitride wide bandgap semiconductors are favorable materials for developing room temperature spintronic devices. The effective manipulation of spin dynamics is a critical request to realize spin field‐effect transistor (FET). In this work, the dependence of the spin relaxation time on external strain‐induced polarization electric field is investigated in InGaN/GaN multiple quantum wells (MQWs) by time‐resolved Kerr rotation spectroscopy. Owing to the almost canceled two different spin–orbit coupling (SOC), the spin relaxation time as long as 311 ps in the MQWs is obtained at room temperature, being much longer than that in bulk GaN. Furthermore, upon applying an external uniaxial strain, the spin relaxation time decreases sensitively, which originates from the breaking of the SU(2) symmetry. The extracted ratio of the SOC coefficients shows a linear dependence on the external strain, confirming the essential role of the polarization electric field. This effective manipulation of the spin relaxation time sheds light on GaN‐based nonballistic spin FET working at room temperature.
Ion Migration‐Induced Amorphization and Phase Segregation as a Degradation Mechanism in Planar Perovskite Solar Cells
Authors: Di Girolamo Diego , Phung Nga , Kosasih Felix Utama , Di Giacomo Francesco , Matteocci Fabio , Smith Joel A. , Flatken Marion A. , Köbler Hans , Turren Cruz Silver H. , Mattoni Alessandro , Cinà Lucio , Rech Bernd , Latini Alessandro , Divitini Giorgio , Ducati Caterina , Di Carlo Aldo , Dini Danilo , Abate Antonio
Published: June 2020

The operation of halide perovskite optoelectronic devices, including solar cells and LEDs, is strongly influenced by the mobility of ions comprising the crystal structure. This peculiarity is particularly true when considering the long‐term stability of devices. A detailed understanding of the ion migration‐driven degradation pathways is critical to design effective stabilization strategies. Nonetheless, despite substantial research in this first decade of perovskite photovoltaics, the long‐term effects of ion migration remain elusive due to the complex chemistry of lead halide perovskites. By linking materials chemistry to device optoelectronics, this study highlights that electrical bias‐induced perovskite amorphization and phase segregation is a crucial degradation mechanism in planar mixed halide perovskite solar cells. Depending on the biasing potential and the injected charge, halide segregation occurs, forming crystalline iodide‐rich domains, which govern light emission and participate in light absorption and photocurrent generation. Additionally, the loss of crystallinity limits charge collection efficiency and eventually degrades the device performance.
Structural Design of Blue‐to‐Red Thermally‐Activated Delayed Fluorescence Molecules by Adjusting the Strength between Donor and Acceptor
Authors: Che Weilong , Xie Yujun , Li Zhen
Published: June 2020

Owing to the faster response time, wider viewing angle and thinner thickness of organic light emitting diodes (OLEDs) than the conventional displays, the development of high‐efficiency light‐emitting materials has become the focus of attention. In recent years, the TADF materials have aroused widespread attention and experienced rapid development as an emitter in OLEDs, since the maximum internal quantum efficiency can reach 100% theoretically. TADF materials have exhibited the potential to be a low‐cost alternative to expensive phosphorescent luminophors. Whereas, the high resolution displays must endow the characteristics of stable and efficient panchromatic emission. The chemical structure of TADF materials are generally composed of electrical donor and acceptor, the emission colors and efficiency can be adjusted by the charge transfer between them. In this paper, TADF emitters with different emission colors are reviewed, accompanied with the investigation on their molecular design strategies and photophysical properties. In addition, the development direction and application of TADF materials are prospected.
CPR News
Authors: Bleemer Russ
Published: June 2020

The International Institute for Conflict Prevention and Resolution in March launched a resource page on its website for conflict resolution in commercial matters when the coronavirus pandemic requires closings and social distancing.
Nature of the Arsonium‐Ylide Ph3As=CH2 and a Uranium(IV) Arsonium–Carbene Complex
Authors: Seed John A. , Sharpe Helen R. , Futcher Harry J. , Wooles Ashley J. , Liddle Stephen T.
Published: June 2020

Treatment of [Ph3EMe][I] with [Na{N(SiMe3)2}] affords the ylides [Ph3E=CH2] (E=As, 1As; P, 1P). For 1As this overcomes prior difficulties in the synthesis of this classical arsonium‐ylide that have historically impeded its wider study. The structure of 1As has now been determined, 45 years after it was first convincingly isolated, and compared to 1P, confirming the long‐proposed hypothesis of increasing pyramidalisation of the ylide‐carbon, highlighting the increasing dominance of E+−C− dipolar resonance form (sp3‐C) over the E=C ene π‐bonded form (sp2‐C), as group 15 is descended. The uranium(IV)–cyclometallate complex [U{N(CH2CH2NSiPri3)2(CH2CH2SiPri2CH(Me)CH2)}] reacts with 1As and 1P by α‐proton abstraction to give [U(TrenTIPS)(CHEPh3)] (TrenTIPS=N(CH2CH2NSiPri3)3; E=As, 2As; P, 2P), where 2As is an unprecedented structurally characterised arsonium‐carbene complex. The short U−C distances and obtuse U‐C‐E angles suggest significant U=C double bond character. A shorter U−C distance is found for 2As than 2P, consistent with increased uranium‐ and reduced pnictonium‐stabilisation of the carbene as group 15 is descended, which is supported by quantum chemical calculations.
Multifunctional Active‐Center‐Transferable Platinum/Lithium Cobalt Oxide Heterostructured Electrocatalysts towards Superior Water Splitting
Authors: Zheng Xiaobo , Cui Peixin , Qian Yumin , Zhao Guoqiang , Zheng Xusheng , Xu Xun , Cheng Zhenxiang , Liu Yuanyue , Dou Shi Xue , Sun Wenping
Published: June 2020

Designing cost‐effective and efficient electrocatalysts plays a pivotal role in advancing the development of electrochemical water splitting for hydrogen generation. Herein, multifunctional active‐center‐transferable heterostructured electrocatalysts, platinum/lithium cobalt oxide (Pt/LiCoO2) composites with Pt nanoparticles (Pt NPs) anchored on LiCoO2 nanosheets, are designed towards highly efficient water splitting. In this electrocatalyst system, the active center can be alternatively switched between Pt species and LiCoO2 for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively. Specifically, Pt species are the active centers and LiCoO2 acts as the co‐catalyst for HER, whereas the active center transfers to LiCoO2 and Pt turns into the co‐catalyst for OER. The unique architecture of Pt/LiCoO2 heterostructure provides abundant interfaces with favorable electronic structure and coordination environment towards optimal adsorption behavior of reaction intermediates. The 30 % Pt/LiCoO2 heterostructured electrocatalyst delivers low overpotentials of 61 and 285 mV to achieve 10 mA cm−2 for HER and OER in alkaline medium, respectively.
Reconciling Electrostatic and n→π* Orbital Contributions in Carbonyl Interactions
Authors: Muchowska Kamila B. , Pascoe Dominic J. , Borsley Stefan , Smolyar Ivan V. , Mati Ioulia K. , Adam Catherine , Nichol Gary S. , Ling Kenneth B. , Cockroft Scott L.
Published: June 2020

Interactions between carbonyl groups are prevalent in protein structures. Earlier investigations identified dominant electrostatic dipolar interactions, while others implicated lone pair n→π* orbital delocalisation. Here these observations are reconciled. A combined experimental and computational approach confirmed the dominance of electrostatic interactions in a new series of synthetic molecular balances, while also highlighting the distance‐dependent observation of inductive polarisation manifested by n→π* orbital delocalisation. Computational fiSAPT energy decomposition and natural bonding orbital analyses correlated with experimental data to reveal the contexts in which short‐range inductive polarisation augment electrostatic dipolar interactions. Thus, we provide a framework for reconciling the context dependency of the dominance of electrostatic interactions and the occurrence of n→π* orbital delocalisation in C=O⋅⋅⋅C=O interactions.
Near‐Infrared‐III‐Absorbing and ‐Emitting Dyes: Energy‐Gap Engineering of Expanded Porphyrinoids via Metallation
Authors: Wang Yue , Ogasahara Koki , Tomihama Daisuke , Mysliborski Radomir , Ishida Masatoshi , Hong Yongseok , Notsuka Yusuke , Yamaoka Yoshihisa , Murayama Tomotaka , Muranaka Atsuya , Uchiyama Masanobu , Mori Shigeki , Yasutake Yuhsuke , Fukatsu Susumu , Kim Dongho , Furuta Hiroyuki
Published: June 2020

The synthesis of organometallic complexes of modified 26π‐conjugated hexaphyrins with absorption and emission capabilities in the third near‐infrared region (NIR‐III) is described. Symmetry alteration of the frontier molecular orbitals (MOs) of bis‐PdII and bis‐PtII complexes of hexaphyrin via N‐confusion modification led to substantial metal dπ–pπ interactions. This MO mixing, in turn, resulted in a significantly narrower HOMO–LUMO energy gap. A remarkable long‐wavelength shift of the lowest S0→S1 absorption beyond 1700 nm was achieved with the bis‐PtII complex, t‐Pt2‐3. The emergence of photoacoustic (PA) signals maximized at 1700 nm makes t‐Pt2‐3 potentially useful as a NIR‐III PA contrast agent. The rigid bis‐PdII complexes, t‐Pd2‐3 and c‐Pd2‐3, are rare examples of NIR emitters beyond 1500 nm. The current study provides new insight into the design of stable, expanded porphyrinic dyes possessing NIR‐III‐emissive and photoacoustic‐response capabilities.
Cross‐Linked Polyphosphazene Hollow Nanosphere‐Derived N/P‐Doped Porous Carbon with Single Nonprecious Metal Atoms for the Oxygen Reduction Reaction
Authors: Wei Xuan , Zheng Diao , Zhao Ming , Chen Hongzhong , Fan Xun , Gao Bin , Gu Long , Guo Yi , Qin Jianbin , Wei Jing , Zhao Yanli , Zhang Guangcheng
Published: June 2020

Heteroatom‐doped polymers or carbon nanospheres have attracted broad research interest. However, rational synthesis of these nanospheres with controllable properties is still a great challenge. Herein, we develop a template‐free approach to construct cross‐linked polyphosphazene nanospheres with tunable hollow structures. As comonomers, hexachlorocyclotriphosphazene provides N and P atoms, tannic acid can coordinate with metal ions, and the replaceable third comonomer can endow the materials with various properties. After carbonization, N/P‐doped mesoporous carbon nanospheres were obtained with small particle size (≈50 nm) and high surface area (411.60 m2 g−1). Structural characterization confirmed uniform dispersion of the single atom transition metal sites (i.e., Co‐N2P2) with N and P dual coordination. Electrochemical measurements and theoretical simulations revealed the oxygen reduction reaction performance. This work provides a solution for fabricating diverse heteroatom‐containing polymer nanospheres and their derived single metal atom doped carbon catalysts.
Building up Strain in One Step: Synthesis of an Edge‐Fused Double Silacyclobutene from an Extensively Trichlorosilylated Butadiene Dianion
Authors: Georg Isabelle , Bursch Markus , Stückrath Julius B. , Alig Edith , Bolte Michael , Lerner Hans‐Wolfram , Grimme Stefan , Wagner Matthias
Published: June 2020

The exhaustive trichlorosilylation of hexachloro‐1,3‐butadiene was achieved in one step by using a mixture of Si2Cl6 and [nBu4N]Cl (7:2 equiv) as the silylation reagent. The corresponding butadiene dianion salt [nBu4N]2[1] was isolated in 36 % yield after recrystallization. The negative charges of [1]2− are mainly delocalized across its two carbanionic (Cl3Si)2C termini (α‐effect of silicon) such that the central bond possesses largely C=C double‐bond character. Upon treatment with 4 equiv of HCl, [1]2− is converted into neutral 1,2,3,4‐tetrakis(trichlorosilyl)but‐2‐ene, 3. The Cl− acceptor AlCl3, induces a twofold ring‐closure reaction of [1]2− to form a six‐membered bicycle 4 in which two silacyclobutene rings are fused along a shared C=C double bond (84 %). Compound 4, which was structurally characterized by X‐ray crystallography, undergoes partial ring opening to a monocyclic silacyclobutene 2 in the presence of HCl, but is thermally stable up to at least 180 °C.
Three‐Dimensional Cuprous Lead Bromide Framework with Highly Efficient and Stable Blue Photoluminescence Emission
Authors: Sun Chen , Guo Ya‐Hui , Han Sha‐Sha , Li Jing‐Zhao , Jiang Kuan , Dong Lin‐Feng , Liu Qi‐Long , Yue Cheng‐Yang , Lei Xiao‐Wu
Published: June 2020

Considering the instability and low photoluminescence quantum yield (PLQY) of blue‐emitting perovskites, it is still challenging and attractive to construct single crystalline hybrid lead halides with highly stable and efficient blue light emission. Herein, by rationally introducing d10 transition metal into single lead halide as new structural building unit and optical emitting center, we prepared a bimetallic halide of [(NH4)2]CuPbBr5 with new type of three‐dimensional (3D) anionic framework. [(NH4)2]CuPbBr5 exhibits strong band‐edge blue emission (441 nm) with a high PLQY of 32 % upon excitation with UV light. Detailed photophysical studies indicate [(NH4)2]CuPbBr5 also displays broadband red light emissions derived from self‐trapped states. Furthermore, the 3D framework features high structural and optical stabilities at extreme environments during at least three years. To our best knowledge, this work represents the first 3D non‐perovskite bimetallic halide with highly efficient and stable blue light emission.
Profiling and Identification of Biocatalyzed Transformation of Sulfoxaflor In Vivo
Authors: Xu Liwei , Guo Lingling , Wang Zhongxing , Xu Xinxin , Zhang Shuang , Wu Xiaoling , Kuang Hua , Xu Chuanlai
Published: June 2020

In the present study, we investigated the biotransformation of the neonicotinoid pesticide sulfoxaflor and the metabolic responses in Sprague‐Dawley rats. Sulfoxaflor transformation was catalyzed by cytochrome P450 while five phase I and four phase II metabolites were identified for the first time in vivo. The experimental results demonstrated that sulfoxaflor brought about the metabolic profiling disturbances in liver and bile. Exposure to sulfoxaflor caused dysregulation of bile acid synthesis and reabsorption by the expression of farnesoid X receptor (FXR). Our data provided insights into biotransformation of chemicals while enabling the implementation of a new toolbox for the design of sulfoximine compounds.
Quantitative Assessment of Tip Effects in Single‐Molecule High‐Speed Atomic Force Microscopy Using DNA Origami Substrates
Authors: Kielar Charlotte , Zhu Siqi , Grundmeier Guido , Keller Adrian
Published: June 2020

High‐speed atomic force microscopy (HS‐AFM) is widely employed in the investigation of dynamic biomolecular processes at a single‐molecule level. However, it remains an open and somewhat controversial question, how these processes are affected by the rapidly scanned AFM tip. While tip effects are commonly believed to be of minor importance in strongly binding systems, weaker interactions may significantly be disturbed. Herein, we quantitatively assess the role of tip effects in a strongly binding system using a DNA origami‐based single‐molecule assay. Despite its femtomolar dissociation constant, we find that HS‐AFM imaging can disrupt monodentate binding of streptavidin (SAv) to biotin (Bt) even under gentle scanning conditions. To a lesser extent, this is also observed for the much stronger bidentate SAv–Bt complex. The presented DNA origami‐based assay can be universally employed to quantify tip effects in strongly and weakly binding systems and to optimize the experimental settings for their reliable HS‐AFM imaging.
Stereodivergent Alkyne Hydrofluorination Using Protic Tetrafluoroborates as Tunable Reagents
Authors: Guo Rui , Qi Xiaotian , Xiang Hengye , Geaneotes Paul , Wang Ruihan , Liu Peng , Wang Yi‐Ming
Published: June 2020

The discovery of safe, general, and practical procedures to prepare vinyl fluorides from readily available precursors remains a synthetic challenge. The metal‐free hydrofluorination of alkynes constitutes an attractive though elusive strategy for their preparation. Introduced here is an inexpensive and easily handled reagent that enables the development of simple and scalable protocols for the regioselective hydrofluorination of alkynes to access both the E and Z isomers of vinyl fluorides. These reaction conditions were suitable for a diverse collection of alkynes, including several highly functionalized pharmaceutical derivatives. Computational and experimental mechanistic studies support C−F bond formation through vinyl cation intermediates, with the E‐ and Z‐hydrofluorination products forming under kinetic and thermodynamic control, respectively.
Twisted Surfaces in Porous Single Crystals to Deliver Enhanced Catalytic Activity and Stability
Authors: Lin Guoming , Li Hao , Xie Kui
Published: June 2020

Porous single crystals which combine ordered lattice structures and disordered inter‐connected pores would provide an alternative to create twisted surface in porous microstructures. Now, transition‐metal nitride Nb4N5 and MoN single crystals are grown on a 2 cm scale to create well‐defined active structures at twisted surfaces. High catalytic activity and stability toward non‐oxidative dehydrogenation of ethane to ethylene is observed. Unsaturated metal–nitrogen coordination structures including Nb‐N1/5, Nb‐N2/5, Mo‐N1/3, and Mo‐N1/6 at the twisted surface mainly account for the C−H activation with chemisorption of H in molecular ethane at the twisted surface, which not only improves dehydrogenation performance but also avoids the deep cracking of ethane to enhance coking resistance. 11–25 % ethane conversion and 98–99 % ethylene selectivity is demonstrated without degradation being observed even after the operation of 50 hours.
Octacyanidorhenate(V) Ion as an Efficient Linker for Hysteretic Two‐Step Iron(II) Spin Crossover Switchable by Temperature, Light, and Pressure
Authors: Chorazy Szymon , Charytanowicz Tomasz , Pinkowicz Dawid , Wang Junhao , Nakabayashi Koji , Klimke Stephen , Renz Franz , Ohkoshi Shin‐ichi , Sieklucka Barbara
Published: June 2020

A two‐step hysteretic FeII spin crossover (SCO) effect was achieved in programmed layered Cs{[Fe(3‐CNpy)2][Re(CN)8]}⋅H2O (1) (3‐CNpy=3‐cyanopyridine) assembly consisting of cyanido‐bridged FeII‐ReV square grid sheets bonded by Cs+ ions. The presence of two non‐equivalent FeII sites and the conjunction of 2D bimetallic coordination network with non‐covalent interlayer interactions involving Cs+, [ReV(CN)8]3− ions, and 3‐CNpy ligands, leads to the occurrence of two steps of thermal SCO with strong cooperativity giving a double thermal hysteresis loop. The resulting spin‐transition phenomenon could be tuned by an external pressure giving the room‐temperature range of SCO, as well as by visible‐light irradiation, inducing an efficient recovery of the high‐spin FeII state at low temperatures. We prove that octacyanidorhenate(V) ion is an outstanding metalloligand for induction of a cooperative multistep, multiswitchable FeII SCO effect.
Direct synthesis of completely unsymmetrical triarylmethanes via Fe(III) salt‐mediated in situ o‐quinone methides process
Authors: Yang Qi , Wu Run‐Shi , Wu Ke‐Xin , Gu Ying‐Chun , Yu Ya‐Qin , Xu Da‐Zhen
Published: June 2020

An efficient and straightforward synthetic approach to completely unsymmetrical triarylmethanes through the situ‐generated o‐quinone methides from readily available starting materials has been successfully developed. In the presence of an Fe(III) salt, three different aromatic rings, including salicylaldehydes, arylboronic acids, and arenes, were incorporated into one molecule in a single step under the base/ligand‐free conditions. The related reactions show high chemoselectivity and afford a variety of completely unsymmetrical triarylmethane products in good to excellent yields.
Purple subphthalocyanine‐phthalocyanine dyad: Synthesis, photophysicochemical properties and DFT study
Authors: Makhseed Saad , Ghazal Basma , Durmuş Mahmut
Published: June 2020

A new phthalocyanine‐subphthalocyanine heterodyad (5) was prepared by Pd(0)‐catalyzed Sonogashira coupling reaction between an asymmetrical phthalocyanine (3) bearing monoiodo and multiple triazolide moieties on its backbone and a subphthalocyanine (4) bearing axially propargyl group. The structure of this heterodyad (5) was subsequently confirmed by the conventional spectroscopic techniques. The photophysical and photochemical properties including; fluorescence and singlet oxygen generation of (5) along with its building chromophores (3) and (4) were also investigated. Interestingly, a purple colored solution was observed by this novel dyad which was significantly different from those colors (green or blue) obtained by phthalocyanine‐subphthalocyanine conjugates. Based on steady state absorption spectroscopic data and transient absorption results, the synthesized dyad 5 was free of aggregation and there is good energy transfer occurs between Pc and subPc moieties. This result was confirmed using density functional theory (DFT) and time‐dependent DFT (TDDFT) analyses: B3LYP exchange‐correlation functional and the 6–31 + G(d) basis set.
A green, efficient and recoverable CeO2/MWCNT nanocomposite catalyzed click synthesis of pyridine‐3‐carboxamides
Authors: Harikrishna Singamsetty , Robert Alice R. , Ganja Himavathi , Maddila Suresh , Jonnalagadda Sreekantha B.
Published: June 2020

A facile, green and environmentally‐friendly protocol for the preparation of ceria doped multi‐walled carbon nanotubes (2.5%CeO2/MWCNTs) composite catalysts are developed. The synthesized catalyst materials have been characterized by using P‐XRD, SEM, TEM and BET analysis. Further, the composite was utilized as a highly efficient and reusable heterogeneous nano‐catalyst for the synthesis of pyridine‐3‐carboxamide derivatives by multicomponent condensation of acetoacetanilide, ammonium acetate, substituted aromatic aldehyde and ethyl cyanoacetate via one‐pot reaction under ethanol solvent conditions at R.T. The remarkable advantages of this green protocol exhibits operational simplicity, easy workup procedure, inexpensive, evading of toxic solvents, shorter reaction times (≤ 15 mins), excellent yields and also avoidance of column chromatography. Furthermore, the catalyst was recyclable and reusability endured for a minimum of six consecutive cycles without significant loss in the catalytic activity.
A parametric simulation on the effect of the rejected brine temperature on the performance of multieffect distillation with thermal vapour compression desalination process and its environmental impacts
Authors: Buabbas Saleh K. , Al‐Obaidi Mudhar A. , Mujtaba Iqbal M.
Published: June 2020

Multieffect distillation with thermal vapour compression (MED–TVC) is one of the most attractive thermal desalination technologies for the production of freshwater. Several mathematical models were presented in the open literature to analyse the steady‐state performance of such process. However, these models have several limitations and assumptions. Therefore, there remains the challenge of having a reliable model to accurately predict the performance of the MED process. Thus, this research attempts to resolve this challenge by rectifying the shortcomings of the models found in the literature and create a new one. The robustness of the developed model is evaluated against the actual data of Umm Al‐Nar commercial plant situated in UAE. In seawater desalinisation, a large amount of high‐salinity stream (brine) is rejected back into the sea. This paper investigates the influence of the rejected (exit) brine temperature on the system performance parameters of MED–TVC process. Specifically, these parameters are considered as total heat consumption, gain output ratio, freshwater production, heat transfer area and performance ratio. Also, the particular parameters of TVC section of the entrainment ratio, compression ratio and expansion ratio are also addressed. Moreover, a critical evaluation of the influence of the rejected brine temperature on the seawater is also embedded.
Bone histology and microanatomy of Edaphosaurus and Dimetrodon (Amniota, Synapsida) vertebrae from the Lower Permian of Texas
Authors: Agliano Amin , Sander P. Martin , Wintrich Tanja
Published: June 2020

Here we describe the histology and microanatomy of vertebral centra of the iconic pelycosaur‐grade synapsids Edaphosaurus boanerges and Dimetrodon spp. Vertebrae from different axial positions and, in the case of Dimetrodon, from different ontogenetic stages were selected. For the histological description, we produced histological petrographic thin sections ground to a thickness of 50–80 μm of the vertebrae in the sagittal and transversal cutting planes. After the preparation process, the thin sections were examined under transmitted and cross‐polarized light in a polarized microscope. The analyzed vertebrae reveal similar bone tissues, where both taxa have cortical parallel‐fibered bone (PFB). PFB and lamellar bone (LB) forms in the cancellous part. However, in juvenile Dimetrodon, woven‐fibered bone (WFB) is also deposited and shows a high degree of vascularity. This suggests that Dimetrodon had slightly faster bone growth than Edaphosaurus, which is mainly made of PFB and LB and shows poorly developed vascular canals. In addition, one specimen of Dimetrodon displays the preservation of an ossified notochord, which can be assumed to be indicative of how the intervertebral tissues were developed. Historically, evidence of how the joint between Dimetrodon vertebral centra was built was lacking until this specimen appeared. If the notochord ran persistently through the vertebrae, it would have possibly increased the stiffness of the vertebral column and would have affected the limbs and locomotion. Furthermore, the organization of trabeculae and relative thickness of the vertebral cortex gives insights into how the animals were adapted to their habitat.
Controlling tractor‐semitrailer vehicles in automated highway systems: Adaptive robust and Lyapunov minimax approach
Authors: Sun Hao , Yang Luwen , Chen Ye‐Hwa , Zhang Xinrong
Published: June 2020

In this paper, we design a coordinated steering and braking control scheme to ensure the tractor‐semitrailer vehicle system is practically stable. The tractor's steering input is designed to realize lane tracking and the semitrailer's differential braking torque is designed to improve the stability of the semitrailer. This control methodology is developed in two steps. Firstly, the expected steering input and the expected differential braking force are derived by introducing a set of given tracking constraints and considering the possible initial condition derivation from the constraints based on the Udwadia‐Kalaba approach. Secondly, we develop an adaptive robust control law to tackle the parameter uncertainty, which may be (possibly) time‐varying, and design the required braking torques, which are the actual inputs, to generate the desired braking forces. Furthermore, this control methodology can deal with nonlinear mechanical systems with both holonomic constraints and nonholonomic constraints. Numerical simulations demonstrate that the control algorithm could guarantee the vehicle dynamics are practically stable and achieve lane following maneuvering.
Affordability Assessments: Policy Recommendations for USEPA
Authors: Mastracchio John , Raucher Robert , Rothstein Eric P. , Clements Janet , Green Zachary
Published: June 2020

Key Takeaways

Affordability challenges affect water sector utilities of all sizes, and they will only increase as the number of income‐limited households grows.

The US Environmental Protection Agency's financial capability assessment has been criticized for not focusing on the most economically vulnerable users and not capturing economic impacts across diverse populations.

A proposed framework displays a more accurate picture of affordability challenges in lower‐income households and provides methods to improve utility and community efforts to accommodate household and utility financial challenges.
Singapore's Water Strategy: Diversified, Robust, and Sustainable
Authors: Seah Harry
Published: June 2020

Key Takeaways

Driven mostly by industrial development, demand for water in the island city‐state of Singapore is expected to almost double by 2060.

The use of reclaimed water (known as NEWater) is the most sustainable and cost‐effective way to boost Singapore's water supply for the long term.

Singapore's national water agency is encouraging companies in water‐intensive industries to implement innovative solutions to improve water sustainability.
Industrial Control Systems: Cyber Policies and Strategies
Authors: Gosine Anil
Published: June 2020

Key Takeaways

A collaborative, all‐hazards approach to preparing for threats to critical infrastructure has enhanced security and resilience in the United States and Canada.

It's up to individual organizations—including water utilities—to have all the elements of an effective security plan in place.

Cybersecurity around industrial control systems needs to keep pace with the sophistication and evolution of attacks on technology environments.

Policies, procedures, risk assessments, and the right technique platforms—all held together by staff knowledge and expertise—create a strong defense.
What Keeps Utility Leaders Up at Night?
Authors: Hughes John , Brown Randal , Dettmer Karen , Donahue John , Margevicius Alex
Published: June 2020

Key Takeaways

In December 2019, AWWA held a full‐day workshop with water utility leaders in Chicago on legal challenges in the water sector.

Lead issues are still top of mind for utility leaders, including lead service line replacements, sampling protocols, corrosion control, and customer communication.

Aging infrastructure is an ongoing concern for many utilities, looming as a potential emergency that affects public health, customer supply, and utility finances.

PFAS, and how to sample for it and communicate about it, is a newer concern among utility leaders.