bluuebunny/crossref_metadata_2025 huggingface dataset:
E‐Selective Hydrothiolation of Terminal Arylallenes with Arylthiols Catalyzed by Ni (PMe3)4
Authors: Ren Shishuai , Xue Benjing , Zheng Tingting , Wang Yangyang , Sun Hongjian , Li Xiaoyan , Fuhr Olaf , Fenske Dieter
Published: December 2019

A catalytic system of regioselective synthesis of allyl sulfides via hydrothiolation of terminal arylallenes with arylthiols has been developed using nickel(0) complex Ni (PMe3)4 as a catalyst. In most cases the excellent to moderate yields were obtained under mild conditions. A catalytic mechanism was suggested and partially‐experimentally verified. To the best of our knowledge, this is the first example of regioselective addition of thiophenols to terminal arylallenes catalyzed by nickel(0) complex. It was noteworthy that this catalytic system was only applicable to thiophenol compounds with terminal arylallenes.
Facile and green synthesis of Cu3V2O8 nanostructures via Moringa peregrina natural extract as a high performance photo catalyst
Authors: Yaghoobi Rahni Soghra , Mohammadzadeh Kakhki Roya
Published: December 2019

In this paper Cu3V2O8 nanoparicles were synthesized with a low‐cost and green method with using the extract of Moringa peregrine. This novel synthesized material was characterized by using X‐ray diffraction (XRD), Field emission scanning electron microscopy (FESEM) and Energy‐dispersive X‐ray spectroscopy (EDS) analysis. The analysis showed the produced nanoparticles have high purity and well crystalline structure. Moreover, the capability of the nanostructures for the removal of dye pollutants was evaluated. For this purpose, methylene blue was selected as a model of organic dye. The experiments showed Cu3V2O8 nanoparticles have high efficiency for removing of dye molecules. Photocatalytic decolorization of methyl blue was optimized with varying the experiment conditions. With 0.02 g of catalyst, pH 6 and concentration of dye 30 mg/l removal efficiency was obtained about 90% in a short time 20 min. Also a kinetic study showed this photodegradation process obeys a first‐order kinetic with rate constant about 0.07 min−1.
Facile synthesis, crystal growth, characterization and computational study of new pyridine‐based halogenated hydrazones: Unveiling the stabilization behavior in terms of noncovalent interactions
Authors: Ali Akbar , Khalid Muhammad , Abid Saba , Iqbal Javed , Tahir Muhammad Nawaz , Rauf Raza Abdul , Zukerman‐Schpector Julio , Paixão Marcio Weber
Published: December 2019

The pyridine‐based halogenated hydrazone derivatives (E)‐N′‐benzylidene‐2‐[(6″‐chloroazin‐2″‐yl)oxy]acetohydrazide (6a), (E)‐N′‐(3′‐chlorobenzylidene)‐2‐[(6″‐chloroazin‐2″‐yl)oxy]acetohydrazide (6b) and (E)‐N′‐(3′‐bromobenzylidene)‐2‐[(6″‐chloroazin‐2″‐yl)oxy]acetohydrazide (6c) have been obtained using 6‐chloro‐2‐hydroxypyridine. The structure of the products (6a–c) has been verified using X‐ray crystallography and spectroscopic approaches. A single‐crystal X‐ray diffraction (SC‐XRD) investigation showed that the structures are stabilized by intermolecular attractive forces. Additionally, density functional theory (DFT) has been adopted to explore the structural properties, vibrational spectra, noncovalent interactions and frontier molecular orbitals using the B3LYP/6‐311 + G(d,p) level. The nonlinear optical properties of the title compounds were calculated using the CAM‐B3LYP/6‐311 + G(d,p) level. Frequency analysis confirmed the stability of the molecules, and an excellent correlation was observed between the DFT‐ and SC‐XRD‐based structural parameters. The SC‐XRD analysis confirmed that the dimers of 6a, 6b and 6c are linked by hydrogen‐bonding interactions. Natural bond orbital (NBO) analysis also reconfirmed the strength of intermolecular hydrogen‐bonding and hyperconjugative interactions. NBO investigation was also utilized to analyze the atomic charges. Moreover, Fourier transform infrared and natural population analyses endorsed that there are significant N&bond;H⋅⋅⋅O&dbond;C hydrogen‐bonding linkages in dimeric structures of the compounds. The hydrogen‐bonding network and different sorts of hyperconjugative interactions are the main reasons for the stability of the products in the solid state. The highest occupied and lowest unoccupied molecular orbital energies and first‐order nonlinear optical properties of these molecules are reported. The quantum chemical parameters were derived using frontier molecular orbital energies.
Prognostic analysis of postoperative clinically nonmetastatic renal cell carcinoma
Authors: Shao Yanxiang , Xiong Sanchao , Sun Guangxi , Dou Weichao , Hu Xu , Yang Weixiao , Lia Thongher , Deng Shi , Wei Qiang , Zeng Hao , Li Xiang
Published: December 2019

Objectives

To investigate the survival characteristics of postoperative nonmetastatic renal cell carcinoma (RCC) patients, and the predictive value of a prognostic model.

Materials and Methods

We retrospectively evaluated data from 1202 postoperative nonmetastatic RCC patients who were treated between 1999 and 2012 at West China Hospital, Sichuan University (Chengdu, China). In addition, we also evaluated data relating to 53 205 cases acquired from the Surveillance, Epidemiology, and End Results (SEER) program. Survival analysis was performed on the cases, and subgroups, using the Kaplan‐Meier and Cox regression methods. The concordance index of the Stage Size Grade Necrosis (SSIGN), Leibovich, and the UCLA integrated staging system, scores was determined to evaluate the accuracy of these outcome prediction models.

Results

The 5‐year overall survival rate for RCC cases in West China Hospital was 87.6%; this was higher than that observed for SEER cases. Survival analysis identified several factors that exerted significant influence over prognosis, including the time of surgery, Eastern Cooperative Oncology Group performance status, tumor stage, size, nuclear differentiation, pathological subtypes, along with necrotic and sarcomatoid differentiation. Moreover tumor stage, size, and nuclear grade were all identified as independent predictors for both our cases and those from the SEER program. Patient groups with advanced RCC, and poorly differentiated RCC subgroups, were both determined to have a poor prognosis. The SSIGN model yielded the best predictive value as a prognostic model, followed by the Leibovich, and UCLA integrated staging system; this was the case for our patients, and for sub‐groups with a poor prognosis.

Conclusion

The prognosis of RCC was mostly influenced by tumor stage, size, and nuclear differentiation. SSIGN may represent the most suitable prognostic model for the Chinese population.
Laser‐Ablation‐Produced Cobalt Nickel Phosphate with High‐Valence Nickel Ions as an Active Catalyst for the Oxygen Evolution Reaction
Authors: Sun Xuechun , Wang Jiaqi , Yin Yuehui , Wang Haibin , Li Shuang , Liu Hui , Mao Jing , Du Xiwen
Published: December 2019

Cost‐effective, highly efficient and stable non‐noble metal‐based catalysts for the oxygen evolution reaction (OER) are very crucial for energy storage and conversion. Here, an amorphous cobalt nickel phosphate (CoNiPO4), containing a considerable amount of high‐valence Ni3+ species as an efficient electrocatalyst for OER in alkaline solution, is reported. The catalyst was converted from Co‐doped Ni2P through pulsed laser ablation in liquid (PLAL) and exhibits a large specific surface area of 162.5 m2 g−1 and a low overpotential of 238 mV at 10 mA cm−2 with a Tafel slope of 46 mV dec−1, which is much lower than those of commercial RuO2 and IrO2. This work demonstrates that PLAL is a powerful technology for generating amorphous CoNiPO4 with high‐valence Ni3+, thus paving a new way towards highly effective OER catalysts.
Concurring Chalcogen‐ and Halogen‐Bonding Interactions in Supramolecular Polymers for Crystal Engineering Applications
Authors: Biot Nicolas , Bonifazi Davide
Published: December 2019

The engineering of crystalline molecular solids through the simultaneous combination of distinctive non‐covalent interactions is an important field of research, as it could allow chemist to prepare materials depicting multi‐responsive properties. It is in this context that, pushed by a will to expand the chemical space of chalcogen‐bonding interactions, a concept is put forward for which chalcogen‐ and halogen‐bonding interactions can be used simultaneously to engineer multicomponent co‐crystals. Through the rational design of crystallizable molecules, chalcogenazolo pyridine scaffold (CGP) modules were prepared that, bearing either a halogen‐bond acceptor or donor at the 2‐position, can interact with suitable complementary molecular modules undergoing formation of supramolecular polymers at the solid state. The recognition reliability of the CGP moiety to form chalcogen‐bonded dimers allows the formation of heteromolecular supramolecular polymers through halogen‐bonding interactions, as confirmed by single‐crystal X‐ray diffraction analysis.
Cancer‐Cell‐Specific Drug Delivery by a Tumor‐Homing CPP‐Gossypol Conjugate Employing a Tracelessly Cleavable Linker
Authors: Maity Suman Kumar , Stahl Paul , Hensel Astrid , Knauer Shirley , Hirschhäuser Christoph , Schmuck Carsten
Published: December 2019

Tumor‐targeted drug delivery is highly important for improving chemotherapy, as it reduces the dose of cytotoxic agents and minimizes the death of healthy tissues. Towards this goal, a conjugate was synthesized of gossypol and a MCF‐7 cancer cell specific CPP (cell penetrating peptide), thus providing a selective drug delivery system. Utilizing the aldehyde moiety of gossypol, the tumor homing CPP RLYMRYYSPTTRRYG was attached through a semi‐labile imine linker, which was cleaved in a traceless fashion under aqueous conditions and had a half‐life of approximately 10 hours. The conjugate killed MCF‐7 cells to a significantly greater extent than HeLa cells or healthy fibroblasts.
Synthesis of Giant π‐Extended Molecular Macrocyclic Rings as Finite Models of Carbon Nanotubes Displaying Enriched Size‐Dependent Physical Properties
Authors: Jia Hongxing , Zhuang Guilin , Huang Qiang , Wang Jinyi , Wu Yayu , Cui Shengsheng , Yang Shangfeng , Du Pingwu
Published: December 2019

Bottom‐up synthesis of π‐extended macrocyclic carbon rings is promising for constructing length‐ and diameter‐specific carbon nanotubes (CNTs). However, it is still a great challenge to realize size‐controllable giant carbon macrocycles. Herein, a tunable synthesis of curved nanographene‐based giant π‐extended macrocyclic rings (CHBC[n]s; n=8, 6, 4), as finite models of armchair CNTs, is reported. Among them, CHBC[8] contains 336 all‐carbon atoms and is the largest cyclic conjugated molecular CNT segment ever reported. CHBC[n]s were systematically characterized by various spectroscopic methods and applied in photoelectrochemical cells for the first time. This revealed that the proton chemical shifts, fluorescence, and electronic and photoelectrical properties of CHBC[n]s are highly dependent on the macrocycle diameter. The tunable bottom‐up synthesis of giant macrocyclic rings could pave the way towards large π‐extended diameter‐ and chirality‐specific CNT segments.
Controlling the Ring‐Opening Polymerization Process Using External Stimuli
Authors: Chen Min , Chen Changle
Published: December 2019

Through the incorporation of stimuli‐responsive units, the properties of ring‐opening polymerization catalysts can be efficiently modulated using external stimuli. This article summarizes some of the recently reported strategies that control the ring‐opening polymerization of cyclic type monomers, using allosteric, redox, Lewis acid/base, supramolecular, electrochemical and light stimuli. These strategies enable the fine tuning of the polymerization process and the microstructure/composition of the final polymeric products.
Universal Algorithm for Simulating and Evaluating Cyclic Voltammetry at Macroporous Electrodes by Considering Random Arrays of Microelectrodes
Authors: Tichter Tim , Schneider Jonathan , Andrae Dirk , Gebhard Marcus , Roth Christina
Published: December 2019

An algorithm for the simulation and evaluation of cyclic voltammetry (CV) at macroporous electrodes such as felts, foams, and layered structures is presented. By considering 1D, 2D, and 3D arrays of electrode sheets, cylindrical microelectrodes, hollow‐cylindrical microelectrodes, and hollow‐spherical microelectrodes the internal diffusion domains of the macroporous structures are approximated. A universal algorithm providing the time‐dependent surface concentrations of the electrochemically active species, required for simulating cyclic voltammetry responses of the individual planar, cylindrical, and spherical microelectrodes, is presented as well. An essential ingredient of the algorithm, which is based on Laplace integral transformation techniques, is the use of a modified Talbot contour for the inverse Laplace transformation. It is demonstrated that first‐order homogeneous chemical kinetics preceding and/or following the electrochemical reaction and electrochemically active species with non‐equal diffusion coefficients can be included in all diffusion models as well. The proposed theory is supported by experimental data acquired for a reference reaction, the oxidation of [Fe(CN)6]4− at platinum electrodes as well as for a technically relevant reaction, the oxidation of VO2+ at carbon felt electrodes. Based on our calculation strategy, we provide a powerful open source tool for simulating and evaluating CV data implemented into a Python graphical user interface (GUI).
Ternary Hybrid Aerogels of g‐C3N4/α‐Fe2O3 on a 3D Graphene Network: An Efficient and Recyclable Z‐Scheme Photocatalyst
Authors: Kim Chansol , Cho Kyeong Min , Park Kangho , Kim Kyoung Hwan , Gereige Issam , Jung Hee‐Tae
Published: December 2019

A Z‐scheme graphitic carbon nitride (g‐C3N4)/α‐Fe2O3 has been incorporated into a three‐dimensional porous graphene aerogel. Graphene aerogels are a promising framework in their use for practical photocatalysis by abundant reaction sites, efficient mass transport of reactants and recyclability through their free‐standing framework. At the same time, Z‐scheme charge transfer among g‐C3N4, α‐Fe2O3, and conductive graphene inhibits the rapid recombination of the photoinduced electrons and holes. Ternary g‐C3N4/α‐Fe2O3/graphene aerogels (CNFGA) showed significantly enhanced photocatalytic activity which demonstrated 4.75 times greater methylene blue degradation and 17.5 times higher photocurrent density than those of exfoliated g‐C3N4 under visible light. In addition, CNFGA exhibited a robust photostability with a simple recovery method while showing only a ca. 2 % decrease in photocatalytic performance after five cycles. These results suggest that this ternary Z‐scheme photocatalyst based on a graphene aerogel has potential use in practical photocatalysis for various environmental applications.
Surgical revascularization and reconstruction procedures in diabetic foot ulceration
Authors: Houlind Kim
Published: December 2019

This article summarizes surgical procedures for preservation of the foot in diabetic patients with peripheral artery disease. Distal bypass surgery performed to perigeniculate arteries and to an isolated ‘blind’ popliteal segment with visible collaterals can be performed with limb salvage rates close to what can be achieved with standard bypass to crural arteries. This is also the case when performing bypass to the dorsalis pedis artery. Bypass to the medial or lateral plantar artery or to the lateral tarsal artery is associated with a relatively high rate of early occlusion, but in the patients who have persistently open grafts, limb salvage is common. The use of an arteriovenous fistula as an adjunct to distal bypass surgery does not improve prognosis. Venous arterialization, either creating retrograde perfusion of the superficial or of the deep veins of the foot has been successful in several cases although it is difficult to predict which patients will benefit. Reconstructive surgery is often performed in a multidisciplinary team including plastic surgeons. In patients with need of more extensive cover of defects, the transplant of muscular or fasciocutaneous free flaps has provided good results in the few centres that have applied this technique. This procedure can be combined with a revascularization in the same session or at a later stage. A majority of the described techniques can be implemented in most vascular centres and they should be considered in complicated cases when standard methods of revascularization and reconstruction do not suffice.
Attention allocation to illness‐compatible information discriminates women with active versus weight‐recovered anorexia nervosa
Authors: Giel Katrin E. , Conzelmann Annette , Renner Tobias J. , Richter Tabea , Martin Benito Sebastian , Zipfel Stephan , Schag Kathrin
Published: December 2019

Objective

Biased attention for disorder‐relevant information plays a crucial role in the maintenance of different mental disorders including eating disorders and might be of use to define recovery beyond symptom‐related criteria.

Method

We assessed attention deployment using eye tracking in a cued choice viewing paradigm to two different categories of disorder‐relevant stimuli in 24 individuals with acute anorexia nervosa (AN), 20 weight‐recovered individuals with a history of AN (WRAN) and 23 healthy control participants (CG). Picture pairs consisted of a food stimulus or a picture depicting physical activity and a matched control stimulus (household item/physical inactivity). Participants rated the valence of stimuli afterwards.

Results

The groups did not differ in initial attention deployment. In later processing stages, AN patients showed a generalized attentional avoidance of food and control pictures as compared to CG, while WRAN individuals were in between. AN patients showed an attentional bias toward physical activity pictures as compared to WRAN individuals, but not the CG. AN individuals rated the food pictures and the pictures showing physical inactivity as less pleasant than the CG, while WRAN individuals were in between.

Discussion

Attention deployment is partly changed in WRAN as compared to the acute AN group, especially with regard to a shift away from illness‐compatible stimuli (physical activity), and this might be a useful recovery criterion. Valence rating of food stimuli might be an additional useful tool to distinguish between acutely ill and weight‐recovered individuals. Attentional biases for illness‐compatible stimuli might qualify as a valuable approach to defining recovery in AN.
Assessing the growth and climate sensitivity of secondary forests in highly deforested Amazonian landscapes
Authors: Elias Fernando , Ferreira Joice , Lennox Gareth D. , Berenguer Erika , Ferreira Socorro , Schwartz Gustavo , Melo Lia de Oliveira , Reis Júnior Denilson N. , Nascimento Rodrigo O. , Ferreira Fabrício Nascimento , Espirito‐Santo Fernando , Smith Charlotte C. , Barlow Jos
Published: December 2019

Tropical forests hold 30% of Earth’s terrestrial carbon and at least 60% of its terrestrial biodiversity, but forest loss and degradation are jeopardizing these ecosystems. Although the regrowth of secondary forests has the potential to offset some of the losses of carbon and biodiversity, it remains unclear if secondary regeneration will be affected by climate changes such as higher temperatures and more frequent extreme droughts. We used a data set of 10 repeated forest inventories spanning two decades (1999–2017) to investigate carbon and tree species recovery and how climate and landscape context influence carbon dynamics in an older secondary forest located in one of the oldest post‐Columbian agricultural frontiers in the Brazilian Amazon. Carbon accumulation averaged 1.08 Mg·ha−1·yr−1, and species richness was effectively constant over the studied period. Moreover, we provide evidence that secondary forests are vulnerable to drought stress: Carbon balance and growth rates were lower in drier periods. This contrasts with drought responses in primary forests, where changes in carbon dynamics are driven by increased stem mortality. These results highlight an important climate change–vegetation feedback, whereby the increasing dry‐season lengths being observed across parts of Amazonia may reduce the effectiveness of secondary forests in sequestering carbon and mitigating climate change. In addition, the current rate of forest regrowth in this region was low compared with previous pan‐tropical and Amazonian assessments—our secondary forests reached just 41.1% of the average carbon and 56% of the tree diversity in the nearest primary forests—suggesting that these areas are unlikely to return to their original levels on politically meaningful time scales.
Functional losses in ground spider communities due to habitat structure degradation under tropical land‐use change
Authors: Potapov Anton M. , Dupérré Nadine , Jochum Malte , Dreczko Kerstin , Klarner Bernhard , Barnes Andrew D. , Krashevska Valentyna , Rembold Katja , Kreft Holger , Brose Ulrich , Widyastuti Rahayu , Harms Danilo , Scheu Stefan
Published: December 2019

Deforestation and land‐use change in tropical regions result in habitat loss and extinction of species that are unable to adapt to the conditions in agricultural landscapes. If the associated loss of functional diversity is not compensated by species colonizing the converted habitats, extinctions might be followed by a reduction or loss of ecosystem functions including biological control. To date, little is known about how land‐use change in the tropics alters the functional diversity of invertebrate predators and which key environmental factors may mitigate the decline in functional diversity and predation in litter and soil communities. We applied litter sieving and heat extraction to study ground spider communities and assessed structural characteristics of vegetation and parameters of litter in rainforest and agricultural land‐use systems (jungle rubber, rubber, and oil palm monocultures) in a Southeast Asian hotspot of rainforest conversion: Sumatra, Indonesia. We found that (1) spider density, species richness, functional diversity, and community predation (energy flux to spiders) were reduced by 57–98% from rainforest to oil palm monoculture; (2) jungle rubber and rubber monoculture sustained relatively high diversity and predation in ground spiders, but small cryptic spider species strongly declined; (3) high species turnover compensated losses of some functional trait combinations, but did not compensate for the overall loss of functional diversity and predation per unit area; (4) spider diversity was related to habitat structure such as amount of litter, understory density, and understory height, while spider predation was better explained by plant diversity. Management practices that increase habitat‐structural complexity and plant diversity such as mulching, reduced weeding, and intercropping monocultures with other plants may contribute to maintaining functional diversity of and predation services provided by ground invertebrate communities in plantations.
Overexpression of GILZ in macrophages limits systemic inflammation while increasing bacterial clearance in sepsis in mice
Authors: Ellouze Mehdi , Vigouroux Lola , Tcherakian Colas , Woerther Paul‐Louis , Guguin Aurélie , Robert Olivier , Surenaud Mathieu , Tran Thi , Calmette Joseph , Barbin Thomas , Perlemuter Gabriel , Cassard Anne‐Marie , Launay Pierre , Maxime Virginie , Annane Djillali , Levy Yves , Godot Véronique
Published: December 2019

Studies support the beneficial effects of glucocorticoids (GCs) during septic shock, steering research toward the potential role of GC‐induced proteins in controlling excessive inflammatory responses. GILZ is a glucocorticoid‐induced protein involved in the anti‐inflammatory effects of GCs. We investigated whether the overexpression of GILZ specifically limited to monocytes and macrophages (M/M) alone could control inflammation, thus improving the outcome of septic shock in animal models. We also monitored the expression of GILZ in M/M from septic mice and septic‐shock patients. M/M from patients and septic mice displayed significantly lower expression of GILZ than those isolated from controls. Furthermore, transgenic mice (Tg‐mice) experiencing sepsis, with increased expression of GILZ restricted to M/M, showed lower frequencies of inflammatory monocytes than their littermates and lower plasma levels of inflammatory cytokines. Tg‐mice also had lower blood bacterial counts. We further established that the upregulation of GILZ in M/M enhanced their phagocytic capacity in in vivo assays. The increase of GILZ in M/M was also sufficient to improve the survival rates of septic mice. These results provide evidence for a central role of both GILZ and M/M in the pathophysiology of septic shock and a possible clue for the modulation of inflammation in this disease.
Synthesis of N,P‐Disecondary o‐Arylphosphanylanilines via o‐R1NHC6H4P(R)O2Et Precursors and Preliminary Study of Cyclocondensations with (EtO)3CH/NH4PF6
Authors: Aluri Bhaskar R. , Ghalib Mohammed , Jones Peter G. , Frauendorf Holm , Heinicke Joachim W.
Published: December 2019

N‐Secondary o‐aminophenylarylphosphinates were prepared by Pd‐catalyzed cross coupling of aryl‐P(OEt)2 with the corresponding o‐bromoanilines and reduced with LiAlH4 to o‐phosphanylanilines. For the N‐mesityl compounds a two‐step reduction was necessary because of competing P–N condensation reactions. Preliminary studies of cyclocondensations of o‐(RPH)C6H4NHR1 with (EtO)3CH/NH4PF6 showed that, in contrast to benzimidazolium salts, accessible in this way from disecondary o‐phenylenediamines, the homologous 1,3‐benzazaphospholium salts are highly reactive and undergo instantaneous oxidative addition of EtOH, liberated in the condensation. The resulting 3‐ethoxy‐benzazaphospholinium salts, which for R = Ph, R1 = Np are relatively stable and were detected by NMR and HRMS, decompose to yield P‐oxo‐1,3‐benzazaphospholine·xHPF6 salts, and for R1 = Me additionally the rearranged N‐ethyl‐P‐oxo‐benzazaphospholinium salt. Detection of triethylphosphate indicates partial acid‐catalyzed conversion of PF6– with EtOH. Alternative cyclocondensation of o‐(MesPH)C6H4NHNp with excess Me2NCH(OMe)2 in the presence of HCl/Et2O led to the 2‐methoxy‐, or after removal of MeOH under vacuum to the corresponding 2‐dimethylamino‐1,3‐benzazaphospholine. The structure elucidation of the new compounds is based on multinuclear NMR data and confirmed for an o‐anilinophenylphosphinate by crystal structure analysis.
Seismic fragility assessment of nonstructural components in unreinforced clay brick masonry buildings
Authors: Derakhshan Hossein , Walsh Kevin Q. , Ingham Jason M. , Griffith Michael C. , Thambiratnam David P.
Published: December 2019

The results of an investigation of the probability of earthquake damage to nonstructural unreinforced masonry (URM) components are presented. The components include parapets, chimneys, and out‐of‐plane loaded facades typical of low‐rise pre‐1940 construction in Australia and New Zealand. The study is based on a street survey of component geometry, in situ data on material strength, and simplified mechanical models. Uncertainties in capacity and demand were quantified based on, respectively, stochastic and deterministic approaches. The damage probabilities were compared with relevant guidelines and empirical damage data from three earthquakes. The study established a link between the qualitative damage states reported in existing guidelines and the quantitative URM component damage states. While some median damage state thresholds correlated well with the data from the guidelines, a larger dispersion value was found in the current study due to the large variations in component properties. Comparisons with empirical data suggest that the developed fragility data provide a realistic estimate of nonstructural component damage that occurred in similar buildings, with a reasonable level of conservatism. The outcome is useful in rapid assessment of the seismic risks due to nonstructural component collapse in URM precincts.
Optimization of face flexible bolting and grouting technology for longwall face support under difficult geological conditions
Authors: Yang Shengli , Li Meng , Song Gaofeng , Yang Yi , Xie Fei
Published: December 2019

Longwall face fall in the open face area is one of the most difficult ground control problems in mining thick coal seams in China especially under difficult geological conditions. This paper has proposed a new flexible bolting and grouting technology for face support. The flexible support method includes face support using flexible coir ropes and face grouting with cement and accelerator mixtures. Numerical and laboratory studies of pullout tests are performed to further improve the flexible support performance including optimization of boreholes and flexible bolts diameters, and selection of grouting materials. The results show that (a) The optimized rope‐borehole diameter ratio is around 0.5 to ensure the best face reinforcement; (b) The grouting material (a mixture of ultrafine cement, mineral powder and sodium silicate) shows advantages of low cost, effective waste disposal, reduced setting time, and good pullout limit force and is recommended for industrial application with sodium silicate at a proportion of 10% by weight and mineral powder at 30%. The application of the new flexible bolting and grouting method in Chenmanzhuang mine shows improved face stability and reduced capital cost.
A review on spectral converting nanomaterials as a photoanode layer in dye‐sensitized solar cells with implementation in energy storage devices
Authors: Mehra Sonali , Bishnoi Swati , Jaiswal Ankit , Jagadeeswararao Metikoti , Srivastava Avinash K. , Sharma Shailesh N. , Vashishtha Parth
Published: December 2019

The present review article aims at the application of rare‐earth‐based titanium dioxide nanocrystals as spectral converters in photovoltaic devices, with special focus on dye‐sensitized solar cells (DSSCs). Additionally, the implementation of DSSCs in energy storage, more importantly, DSSCs and lithium‐ion batteries (LIB) integrated devices are systematically described. The absorption in DSSCs is mainly confined to the visible solar spectrum, which is one of the main reasons behind its limited power conversion efficiency. This has led to shifting of research focus on broadening the light absorption range of DSSCs, which can further lead to enhancement in overall power conversion efficiency. TiO2, doped with rare‐earth (RE) ions, is often used as an electron transport layer (ETL) in DSSCs to overcome this absorption‐related issue. This article gives a detailed review of TiO2 doped with different RE ions, as an electron transport layer in DSSCs. More importantly, we have summarized all the recent important findings with the application of DSSCs in LIB and photocapacitors.
Forecasting under model uncertainty: Non‐homogeneous hidden Markov models with Pòlya‐Gamma data augmentation
Authors: Koki Constandina , Meligkotsidou Loukia , Vrontos Ioannis
Published: December 2019

We consider finite state‐space non‐homogeneous hidden Markov models for forecasting univariate time series. Given a set of predictors, the time series are modeled via predictive regressions with state‐dependent coefficients and time‐varying transition probabilities that depend on the predictors via a logistic/multinomial function. In a hidden Markov setting, inference for logistic regression coefficients becomes complicated and in some cases impossible due to convergence issues. In this paper, we aim to address this problem utilizing the recently proposed Pólya‐Gamma latent variable scheme. Also, we allow for model uncertainty regarding the predictors that affect the series both linearly — in the mean — and non‐linearly — in the transition matrix. Predictor selection and inference on the model parameters are based on an automatic Markov chain Monte Carlo scheme with reversible jump steps. Hence the proposed methodology can be used as a black box for predicting time series. Using simulation experiments, we illustrate the performance of our algorithm in various setups, in terms of mixing properties, model selection and predictive ability. An empirical study on realized volatility data shows that our methodology gives improved forecasts compared to benchmark models.
Therapeutic alternative of the ketogenic Mediterranean diet to improve mitochondrial activity in Amyotrophic Lateral Sclerosis (ALS): A Comprehensive Review
Authors: Caplliure‐Llopis Jordi , Peralta‐Chamba Thalía , Carrera‐Juliá Sandra , Cuerda‐Ballester María , Drehmer‐Rieger Eraci , López‐Rodriguez María Mar , de la Rubia Ortí Jose Enrique
Published: December 2019

Amyotrophic lateral sclerosis (ALS) is an incurable neurodegenerative disease which is pathogenically based on the mitochondrial alteration of motor neurons, causing progressive neuron death. While ALS is characterized by enormous oxidative stress, the Mediterranean diet has been seen to have high antioxidant power. Therefore, the aim of this study is to determine how the Mediterranean diet can improve mitochondrial activity, establishing the specific nutrients and, in addition, observing the pathogenic mechanisms related to the disease that would achieve this improvement. To this end, a comprehensive review of the literature was performed using PubMed. KBs have been observed to have a neuroprotective effect to improve energy balance, increasing survival and the number of motor neurons. This ketogenesis can be achieved after following a Mediterranean diet which is associated with great benefits in other neurodegenerative diseases such as Alzheimer's disease, Parkinson's disease, and ALS. These benefits are due to the high antioxidant power especially based on polyphenols contained mainly in olive oil, wine, nuts, or berries. In short, KBs could be considered as a promising option to treat ALS, representing an alternative source to glucose in motor neurons by providing neuroprotection. In addition, treatment results can be improved as ketogenesis can be achieved (increase in KBs) by following a Mediterranean diet, thanks to the high antioxidant properties which, at the same time, would improve the high oxidative stress that characterizes the disease.
Mutant C9orf72 human iPSC‐derived astrocytes cause non‐cell autonomous motor neuron pathophysiology
Authors: Zhao Chen , Devlin Anna‐Claire , Chouhan Amit K. , Selvaraj Bhuvaneish T. , Stavrou Maria , Burr Karen , Brivio Veronica , He Xin , Mehta Arpan R. , Story David , Shaw Christopher E. , Dando Owen , Hardingham Giles E. , Miles Gareth B. , Chandran Siddharthan
Published: December 2019

Mutations in C9orf72 are the most common genetic cause of amyotrophic lateral sclerosis (ALS). Accumulating evidence implicates astrocytes as important non‐cell autonomous contributors to ALS pathogenesis, although the potential deleterious effects of astrocytes on the function of motor neurons remains to be determined in a completely humanized model of C9orf72‐mediated ALS. Here, we use a human iPSC‐based model to study the cell autonomous and non‐autonomous consequences of mutant C9orf72 expression by astrocytes. We show that mutant astrocytes both recapitulate key aspects of C9orf72‐related ALS pathology and, upon co‐culture, cause motor neurons to undergo a progressive loss of action potential output due to decreases in the magnitude of voltage‐activated Na+ and K+ currents. Importantly, CRISPR/Cas‐9 mediated excision of the C9orf72 repeat expansion reverses these phenotypes, confirming that the C9orf72 mutation is responsible for both cell‐autonomous astrocyte pathology and non‐cell autonomous motor neuron pathophysiology.
Defining Temporally Dynamic Life Cycle Assessment: A Review
Authors: Sohn Joshua , Kalbar Pradip , Goldstein Benjamin , Birkved Morten
Published: December 2019

Durable goods last for years, decades, or even centuries. The environmental implications of the changing social, economic, and material conditions in which these goods are embedded can be overlooked by conventional life cycle assessment (LCA) that assumes a static world. To avoid this oversight, methods such as dynamic LCA (DLCA) are increasingly being used. Despite the growing use of DLCA, numerous questions remain, including how this dynamism is incorporated and what aspects of any given DLCA are dynamic. To answer these questions, we performed a review of 56 DLCAs, of which 44 propose a framework for DLCA covering all International Organization for Standardization phases of an LCA or that carry out a DLCA. Three types of LCA dynamism are identified and assessed for the reviewed literature: dynamic process inventory, dynamic systems, and dynamic characterization, while a further 2 types of LCA dynamism, dynamic scope and dynamic weighting, are proposed but not applied in the assessed literature. We found that the implementation of DLCA varies widely, and inventories accounting for dynamic characteristics are by far the most prevalent expression of DLCA. To reduce confusion surrounding the discussion of DLCA, we propose a definition of DLCA and its subtypes: full DLCA, partial DLCA, and prospective LCA. It is concluded that, among the current array of DLCA definitions, the implementation of partially dynamic LCA (PDLCA), which applies dynamism in only some parts of the LCA, is common and likely to continue. This is because PDLCA offers quantifiable marginal utility in terms of increased validity of the assessment, in relation to conventional LCA methods, but caution is needed in applying PDLCA because of potential for introducing bias into the LCA. To avoid this problem, we propose incorporating system dynamism as part of a sensitivity analysis, particularly in PDLCA that are limited by missing data. Integr Environ Assess Manag 2020;16:314–323. © 2019 SETAC

KEY POINTS

The application of dynamism in life cycle assessment varies significantly due to a lack of definition and methodological guidelines. Incorporation of dynamics in a life cycle assessment can significantly alter results. By incorporating dynamism as a type of sensitivity analysis instead of in the reported results, when data are not available to incorporate dynamism in the entire system, inadvertent bias can be avoided while maintaining the benefits of dynamic assessment. We define dynamic life cycle assessment as well as 3 distinct subtypes that were encountered in the literature.
Dual‐channel type tunable field‐effect transistors based on vertical bilayer WS2(1 − x)Se2x/SnS2 heterostructures
Authors: Zheng Biyuan , Li Dong , Zhu Chenguang , Lan Jianyue , Sun Xingxia , Zheng Weihao , Liu Huawei , Zhang Xuehong , Zhu Xiaoli , Feng Yexin , Xu Tao , Sun Litao , Xu Gengzhao , Wang Xiao , Ma Chao , Pan Anlian
Published: December 2019

Layered semiconductor heterostructures are essential elements in modern electronic and optoelectronic devices. Dynamically engineering the composition of these heterostructures may enable the flexible design of the properties of heterostructure‐based electronics and optoelectronics as well as their optimization. Here, we report for the first time a two‐step chemical vapor deposition approach for a series of WS2(1 − x)Se2x/SnS2 vertical heterostructures with high‐quality and large areas. The steady‐state photoluminescence results exhibit an obvious composition‐related quenching ratio, revealing a strong coherence between the band offset and the charge transfer efficiency at the junction interface. Based on the achieved heterostructures, dual‐channel back‐gate field‐effect transistors were successfully designed and exhibited typical composition‐dependent transport behaviors, and pure n‐type unipolar transistors to ambipolar transistors were realized in such systems. The direct vapor growth of these novel vertical WS2(1 − x)Se2x/SnS2 heterostructures could offer an interesting system for probing new physical properties and provide a series of layered heterostructures for high‐quality devices.

image
EVALUATION OF AQUACROP MODEL IN SIMULATING BITTER GOURD WATER PRODUCTIVITY UNDER SALINE IRRIGATION
Authors: Soomro Kamran Baksh , Alaghmand Sina , Shahid Muhammad Rizwan , Andriyas Sanyogita , Talei Amin
Published: December 2019

The agricultural sector, globally, faces multifaceted challenges to produce more with a minimum amount of water to enhance water productivity (WP). In this regard, crop modelling is an efficient approach for estimating WP and plays a significant role in addressing water management strategies. The present research has been conducted in Malir, Karachi—a semi‐arid region in the Sindh Province of Pakistan. The aim was to evaluate the effects of two different qualities of irrigation water including, fresh quality (IT1 0.56 dS m−1) and saline groundwater (IT2 2.89 dS m−1) on canopy cover (CC), biomass, crop yield and water productivity (WP) of bitter‐gourd. The AquaCrop model was used for the first time for bitter gourd in a semi‐arid region under drip irrigation. Simulations were carried out for two cropping seasons (i.e. season one (summer) and season two (winter). The modelled values were slightly higher than the measured biomass and yield values in both calibration and validation procedures. The performance of the AquaCrop model was estimated through different statistical indicators such as model efficiency (E), root mean square error (RMSE), and index of agreement (dindex). These indicators revealed that the model simulated bitter gourd biomass and crop yield well. In addition, the model's performance was good under all irrigation treatments, with RMSE in the range 1.2–3.7, 0.5–1.8, dindex 0.94–0.98 and E 0.93–0.97. The model also overestimated the biomass and crop yield. Overall, the AquaCrop model overestimated biomass and crop yield for both seasons. © 2019 John Wiley & Sons, Ltd.
In vivo efficacy of calcium phosphate‐based synthetic‐bone‐mineral on bone loss resulting from estrogen and mineral deficiencies
Authors: Srinivasan Kritika , Mijares Dindo Q. , Janal Malvin N. , Aranya Anupama K. , Zhang Denzil S. , LeGeros Racquel Z. , Zhang Yu
Published: December 2019

Osteopenia and osteoporosis affect over 40 million US adults 50 years and older. Both diseases are strongly influenced by estrogen and nutritional–mineral deficiencies. This study investigates the efficacy of orally delivered synthetic‐bone‐mineral (SBM), a newly developed calcium phosphate based biomaterial, on reversing bone loss induced by these two critical deficiencies. Thirty 3‐month‐old female rats were randomly allocated to either control—sham surgery on normal diet; or one of the four experimental groups: Sham surgery on a low mineral diet (LMD), ovariectomized (OVX) on LMD, OVX on LMD with SBM with/without fluoride (F). The rats were sacrificed after 6 months, at 9‐month‐old. After 6 months, although all groups lost bone mineral density relative to controls, the supplemented OVX rats showed higher bone mineral density than their unsupplemented counterparts. The 2 SBM supplemented groups improved bone loading capacity by 28.1 and 35.4% compared to the OVX LMD group. Bones from supplemented rats exhibited higher inorganic/organic ratios. The addition of F did not have a significant influence on bone loss. Our findings suggest that SBM supplement is effective in maintaining bone health and offsetting the deleterious effects of estrogen and/or mineral deficiencies on bone density, microarchitecture, and strength.
Continuous conversion of CO2to alcohols in a TiO2photoanode‐driven photoelectrochemical system
Authors: Castro Sergio , Albo Jonathan , Irabien Angel
Published: December 2019

BACKGROUND

The recycling of CO2by photoelectrochemical reduction has attracted wide interest due to its potential benefits when compared to electro‐ and photo‐catalytic approaches. Among the various available semiconductors, TiO2is the most employed material in photoelectrochemical cells. Besides, Cu is a well‐known electrocatalyst for the production of alcohols from CO2reduction.

RESULTS

A photoelectrochemical cell consisting of a TiO2‐based membrane electrode assembly (MEA) photoanode and a Cu plate is employed to reduce CO2to methanol and ethanol continuously under UV illumination (100 mW cm−2). A maximum increment of 4.3 mA cm−2in current between the illuminated and dark conditions is achieved at −2 VversusAg/AgCl. The continuous photoelectrochemical reduction process in the filter‐press cell is evaluated in terms of reaction rate (r), as well as Faradaic efficiency (FE) and energy efficiency (EE). At −1.8 VversusAg/AgCl, a maximum reaction rate ofr= 9.5 μmol m−2s−1,FE= 16.2% andEE= 5.2% for methanol andr= 6.8 μmol m−2s−1,FE= 23.2% andEE= 6.8% for ethanol can be achieved.

CONCLUSIONS

The potential benefits of the photoanode‐driven system, in terms of yields and efficiencies, are observed when employing a TiO2‐based MEA photoanode and Cu as dark cathode. The results demonstrate first the effect of UV illumination on current density, and then the formation of alcohols from the continuous photoreduction of CO2. Increasing the external applied voltage leads to an enhanced production of methanol, but decreases ethanol formation. The system outperforms previous photoanode‐based systems for CO2‐to‐alcohols reactions. © 2019 Society of Chemical Industry
Development of parallel measures to assess HIV stigma and discrimination among people living with HIV, community members and health workers in the HPTN 071 (PopART) trial in Zambia and South Africa
Authors: Stangl Anne L , Lilleston Pamela , Mathema Hlengani , Pliakas Triantafyllos , Krishnaratne Shari , Sievwright Kirsty , Bell‐Mandla Nomhle , Vermaak Redwaan , Mainga Tila , Steinhaus Mara , Donnell Deborah , Schaap Ab , Bock Peter , Ayles Helen , Hayes Richard , Hoddinott Graeme , Bond Virginia , Hargreaves James R ,   on behalf of the HPTN 071 (PopART) Study Team
Published: December 2019

Introduction

Integrating standardized measures of HIV stigma and discrimination into research studies of emerging HIV prevention approaches could enhance uptake and retention of these approaches, and care and treatment for people living with HIV (PLHIV), by informing stigma mitigation strategies. We sought to develop a succinct set of measures to capture key domains of stigma for use in research on HIV prevention technologies.

Methods

From 2013 to 2015, we collected baseline data on HIV stigma from three populations (PLHIV (N = 4053), community members (N = 5782) and health workers (N = 1560)) in 21 study communities in South Africa and Zambia participating in the HPTN 071 (PopART) cluster‐randomized trial. Forty questions were adapted from a harmonized set of measures developed in a consultative, global process. Informed by theory and factor analysis, we developed seven scales, with values ranging from 0 to 3, based on a 4‐point agreement Likert, and calculated means to assess different aspects of stigma. Higher means reflected more stigma. We developed two measures capturing percentages of PLHIV who reported experiencing any stigma in communities or healthcare settings in the past 12 months. We validated our measures by examining reliability using Cronbach's alpha and comparing the distribution of responses across characteristics previously associated with HIV stigma.

Results

Thirty‐five questions ultimately contributed to seven scales and two experience measures. All scales demonstrated acceptable to very good internal consistency. Among PLHIV, a scale captured internalized stigma, and experience measures demonstrated that 22.0% of PLHIV experienced stigma in the community and 7.1% in healthcare settings. Three scales for community members assessed fear and judgement, perceived stigma in the community and perceived stigma in healthcare settings. Similarly, health worker scales assessed fear and judgement, perceived stigma in the community and perceived co‐worker stigma in healthcare settings. A higher proportion of community members and health workers reported perceived stigma than the proportion of PLHIV who reported experiences of stigma.

Conclusions

We developed novel, valid measures that allowed for triangulation of HIV stigma across three populations in a large‐scale study. Such comparisons will illuminate how stigma influences and is influenced by programmatic changes to HIV service delivery over time.