bluuebunny/crossref_metadata_2025 huggingface dataset:
Investigation of photocatalytic chlorpyrifos degradation by a new silica mesoporous material immobilized by WS2 and Fe3O4 nanoparticles: Application of response surface methodology
Authors: Merci Sanaz , Saljooqi Asma , Shamspur Tayebeh , Mostafavi Ali
Published: January 2020

In the present research, Fe3O4 and WS2 nanoparticles immobilized on or in KIT‐6 (KIT: Korea Institute of Science and Technology) pores (KIT‐6/WS2‐Fe3O4) were synthesized and studied as a photocatalyst for degradation of representative chlorpyrifos as an organophosphorus pesticide. In addition, the KIT‐6/WS2‐Fe3O4 photocatalyst was characterized by different methods such as TEM, FESEM‐EDS‐Mapping, XRD, and N2 adsorption/desorption surface area, in order to understand their morphology, structural, and physical properties. The photocatalytic performance of this photocatalyst was investigated for degradation of chlorpyrifos by visible light irritation. The effects of variables such as chlorpyrifos concentration, KIT‐6/WS2‐Fe3O4 nanocatalyst amount, pH, and irradiation time on chlorpyrifos degradation efficiency was studied by central composite design with response surface methodology. The optimum conditions for CP degradation were obtained by 50 mg KIT‐6/WS2‐Fe3O4 nanocatalyst, and 7.2 ppm chlorpyrifos solution with pH = 6, at 52 min. The pseudo‐first‐order model with rate constants equal to 0.069 min−1 as best choice efficiency described the chlorpyrifos degradation process according to Langmuir‐Hinshelwood kinetic.
Dichloroimidazolidinedione‐activated one‐pot Suzuki–Miyaura cross‐coupling of phenols
Authors: Madankar Kamelia , Mokhtari Javad , Mirjafary Zohreh
Published: January 2020

The first general method for the Suzuki‐type cross‐coupling of phenols with aryl boronic acids using dichloroimidazolidinedione (DCID) as a new reagent is presented. In the presence of DCID and Pd/metal–organic framework (MOF), coupling of aryl boronic acids with a wide range of phenols, was carried out smoothly in tetrahydrofuran (THF) at reflux conditions to afford the cross‐coupling products in good to excellent yields. The structures of all compounds were corroborated by 1H‐ and 13C‐NMR. A plausible mechanism for this type of reaction is proposed.
Benefits of crop diversification in Fiji's sugarcane farming
Authors: Singh Amar
Published: January 2020

The sugar industry has shaped the development of Fiji's economy for over a century; but, for the past 15 years, sugarcane production has been declining. A study was undertaken of over 300 sugarcane farmers in Fiji to determine the benefits of crop diversification and to compare the level of profitability for farmers fully dedicated to sugarcane farming and sugarcane farmers who have diversified. The findings demonstrate that a farmer in the latter group was able to achieve 45% higher profitability than one in the former. Fiji has the potential to increase farm output from diversification, but the relevant stakeholders need to help farmers secure markets and provide appropriate guidance and training.
Pharmacophore modeling, 3D‐QSAR, synthesis, and anti‐lung cancer evaluation of novel thieno[2,3‐d][1,2,3]triazines targeting EGFR
Authors: Elrayess Ranza , Abdel Aziz Yasmine M. , Elgawish Mohamed S. , Elewa Marwa , Elshihawy Hosam A. , Said Mohamed M.
Published: January 2020

Two series of thieno[2,3‐d][1,2,3]triazine derivatives were designed, synthesized, and biologically evaluated as potential epidermal growth factor receptor (EGFR) inhibitors targeting the non‐small‐cell lung cancer cell line H1299. Most of the synthesized compounds displayed IC50 values ranging from 25 to 58 nM against H1299, which are superior to that of gefitinib (40 µM). 3‐(5,6,7,8‐Tetrahydro‐7H‐cyclohexa[4:5]thieno[2,3‐d]‐1,2,3‐triazin‐4‐ylamino)benzene‐1,3‐diamine (6b) achieved the highest cytotoxic activity against H1299 with an IC50 value of 25 nM; it had the ability to decrease the EGFR concentration in H1299 cells from 7.22 to 2.67 pg/ml. In vitro, the IC50 value of compound 6b was 0.33 nM against EGFR, which is superior to that of gefitinib at 1.9 nM and erlotinib at 4 nM. The three‐dimensional quantitative structure–activity relationships and molecular modeling studies revealed comparable binding modes of compound 6b, gefitinib, and erlotinib in the EGFR active site. The in silico ADME (absorption, distribution, metabolism, and excretion) prediction parameters of this compound revealed promising pharmacokinetic and physicochemical properties. Moreover, DFT (density functional theory) calculations showed the high reactivity of compound 6b toward the EGFR compared with other compounds. The designed compound 6b might serve as an encouraging lead compound for the discovery of promising anti‐lung cancer agents targeting EGFR.
Advances in Protecting Groups for Oligosaccharide Synthesis
Authors: Ghosh Bhaswati , Kulkarni Suvarn S.
Published: January 2020

Carbohydrates contain numerous hydroxyl groups and sometimes amine functionalities which lead to a variety of complex structures. In order to discriminate each hydroxyl group for the synthesis of complex oligosaccharides, protecting group manipulations are essential. Although the primary role of a protecting group is to temporarily mask a particular hydroxyl/amino group, it plays a greater role in tuning the reactivity of coupling partners as well as regioselectivity and stereoselectivity of glycosylations. Several protecting groups offer anchimeric assistance in glycosylation. They also alter the solubility of substrates and thereby influence the reaction outcome. Since oligosaccharides comprise branched structures, the glycosyl donors and acceptors need to be protected with orthogonal protected groups that can be selectively removed one at a time without affecting other groups. This minireview is therefore intended to provide a discussion on new protecting groups for amino and hydroxyl groups, which have been introduced over last ten years in the field of carbohydrate synthesis. These protecting groups are also useful for synthesizing non‐carbohydrate target molecules as well.
Intramuscular innervation patterns of the splenius capitis and splenius cervicis and their clinical implications for botulinum toxin injections
Authors: Kwon Hyun‐Jin , Yang Hun‐Mu , Won Sung‐Yoon
Published: January 2020

Introduction

The purpose of this study was to clearly characterize the intramuscular nerve distributions of the splenius capitis and splenius cervicis muscles that are both responsible for the onset of a chronic tension type headache and to use this information to identify the effective botulinum toxin (BoNT) injection sites.

Materials and Methods

Ten splenius capitis and splenius cervicis specimens were subjected to Sihler's staining to reveal intramuscular nerve arborization patterns and determined the optimal location for BoNT injection.

Results

Nerve distribution patterns in the splenius capitis were identified as nerve pathways that travel down toward the origin point and others that travel up toward the insertion point. This neuromuscular innervation from the central (50%) point was distributed evenly in these two directions. The neural pathways of splenius cervicis traveled vertically from the insertion point to the origin point. If the length from the muscle origin point to the insertion point is normalized to 100%, motor neurons innervate the muscle from around the 30% to the 70% point.

Conclusions

The safest and most‐effective BoNT injection sites for the splenius capitis and splenius cervicis were found at around the 50% point and the 30% to the 70% point, respectively.
Location of the infraorbital foramen with reference to soft tissue landmarks for regional nerve blocks during midface surgery
Authors: Shin Kang‐Jae , Shin Hyun Jin , Lee Shin‐Hyo
Published: January 2020

Purpose

An infraorbital nerve (ION) block is widely used to accomplish regional anesthesia during surgical procedures involving the midface region. This study aimed to elucidate the exact location of the infraorbital foramen (IOF) in relation to clinically useful soft‐tissue landmarks for achieving an effective ION block.

Methods

Forty‐three hemifaces from 23 embalmed Korean cadavers were dissected. The lateral canthus, peak of Cupid's bow, medial limbus, and midline were used as reference points. The distances from the IOF to the midline and the lateral canthus were measured.

Results

The IOF was located approximately 25 mm below the lateral canthus and 27 mm lateral to the midline. In all cases, the IOF was situated within 9.0 mm of the crossing point of the oblique line connecting the lateral canthus to the peak of Cupid's bow and the vertical line through the medial limbus.

Conclusion

Considering the spread of an anesthetic agent, injecting it into the crossing point of the oblique line through the lateral canthus to the peak of Cupid's bow and the vertical line through the medial limbus would successfully block the ION in most patients.
Morphology of ejaculatory ducts: A systematic review
Authors: Mathangasinghe Yasith , Samaranayake Udagedara M. J. E. , Dolapihilla Buddhini N , Anthony Dimonge J. , Malalasekera Ajith P.
Published: January 2020

The morphology of human ejaculatory ducts has not been well established. The objective of this study was to describe macroscopic and microscopic anatomy of ejaculatory ducts. We conducted a systematic review using MEDLINE, Scopus, PubMed, and Cochrane databases. Search terms were: “ejaculatory ducts,” “seminal colliculus,” “prostatic utricle,” “anatomy,” “histology,” “radiology,” and “embryology.” We only included studies assessing adult (>18 years) humans published before November 1, 2019. We excluded studies describing pathological ducts and case reports. Independent authors extracted data using predefined criteria. Fourteen studies were included in the qualitative synthesis. Usually, the ejaculatory ducts entered the prostate by piercing the central part of its base. Most studies identified an anteromedial curve of the ducts at the outset within the prostate, their subsequent course being a straight path towards the seminal colliculus, their terminal parts diverging immediately before joining the prostatic urethra. However, the morphology of the terminal part of the ducts was inconsistent. The mean length of the ducts ranged from 1.4 to 2.2 cm. In conclusion, the luminal diameter gradually decreased as the ducts traveled towards the seminal colliculus. Ejaculatory ducts angulate anteromedially at their onset within the prostate and travel straight towards the seminal colliculus. Their terminal parts diverge immediately before joining the prostatic urethra. However, the reported dimensions of the ducts differ among studies.
Integrating Reactors and Catalysts through Three‐Dimensional Printing: Efficiency and Reusability of an Impregnated Palladium on Silica Monolith in Sonogashira and Suzuki Reactions
Authors: Díaz‐Marta Antonio S. , Yañez Susana , Lasorsa Eliana , Pacheco Patricia , Tubío Carmen R. , Rivas José , Piñeiro Yolanda , Gómez Manuel A. Gonzalez , Amorín Manuel , Guitián Francisco , Coelho Alberto
Published: January 2020

For this work, an integrated system composed of a polypropylene reactor and a palladium on silica monolithic catalyst was designed and manufactured by 3D‐printing. These devices are able to perform solution phase chemistry in a robotic orbital shaker. The capped reactor was obtained in its entirety by 3D‐printing, using polypropylene and fused deposition modeling. The monolithic catalyst was also obtained by 3D‐printing ‐robocasting‐ of a silica support, sintering and subsequent palladium deposition through the wet impregnation method. The catalytic efficiency in Sonogashira or Suzuki reactions as well as the recyclability of the entire system – catalyst+reactor – were studied. The strong electrostatic adsorption (SEA) of the palladium on sintered silica and the reduced mechanical stress produced by the convenient adjustment of the catalyst into the polypropylene reactor makes the catalytic system reusable without significant loss of catalytic activity.
Phenomenological Rule from Correlations of Conduction/Valence Band Energies and Bandgap Energies in Semiconductor Photocatalysts: Calcium Bismuthates versus Strontium Bismuthates
Authors: Shtarev D. S. , Ryabchuk V. K. , Rudakova A. V. , Shtareva A. V. , Molokeev M. S. , Kirichenko E. A. , Serpone N.
Published: January 2020

A number of calcium bismuthates were synthesized (25 to 50 mol% in Ca) and characterized by XRD, SEM, EDX, XPS and DRS techniques; the latter provided an estimate of the bandgap energies (Ebg=2.41 to 3.29 eV) via Tauc plots for indirect transitions, whereas XPS established the potentials (vs NHE) of their respective valence bands (and thus the conduction bands). Linear correlations existed between EVB/ECB and Ebg that when compared with those of strontium bismuthates (reported earlier) showed that differences in energies at Ebg=0 eV are related to the difference in the absolute electronegativities of Ca and Sr, from which the following empirical phenomenological rule is postulated: replacing one alkaline earth metal in bismuthates by another causes the points of intersection of the linear correlations ECB(Ebg) and EVB(Ebg) to be displaced by an amount equal to twice the difference in absolute electronegativities of these metals.
Au/Ta(110) and Au/Nb(110) as Highly Active, Stable, and Inexpensive Catalysts for Oxygen Reduction Reaction on Hydrogen Fuel Cell Cathodes: Prediction from First Principles
Authors: Campbell Tyler , Alcántara Ortigoza Marisol , Stolbov Sergey
Published: January 2020

We propose here structures – a gold monolayer on early transition metal surfaces – as a promising alternative to the prohibitively expensive platinum‐based electro‐catalysts for the oxygen reduction reaction (ORR), which occurs on hydrogen fuel cell cathodes. Based on existing knowledge and educated guesses, we preselect Au/Nb, Au/Ta, Au/Mo, and Au/W as potential catalysts. Our calculations show that these materials are stable and have very high dissolution potentials. A deviation from the linear scaling for the binding energy of ORR intermediates, revealed for Au/Nb and Au/Ta, has a desired impact on the ORR thermodynamics. We find it to be a result of hybridization of p‐electronic states of oxygen belonging the OOH‐radical and Au‐pz states. The calculated ORR free energy diagrams show that the ORR onset potentials for Au/Nb and Au/Ta are significantly higher than that for Pt. We thus predict two inexpensive, thermodynamically and electrochemically stable, and highly active ORR catalysts.
Relationship Between Sweat and Blood Lactate Levels During Exhaustive Physical Exercise
Authors: Karpova Elena V. , Laptev Aleksey I. , Andreev Egor A. , Karyakina Elena E. , Karyakin Arkady A.
Published: January 2020

In contrast to the generally accepted view, that sweat lactate is irrelevant to blood, we report on the suitability of sweat lactate for diagnostics. We demonstrate a significant increase in lactate concentration in sweat from the working muscle area simultaneously with the rise of blood lactate content during exhaustive physical exercise. The variation rates of lactate concentration in sweat from working and latent muscle areas correlate positively with blood lactate levels (r>0.8 and r=0.7, respectively), thus offering the prospect of a non‐invasive approach for the monitoring of sportsperson training. Moreover, sweat lactate, being the faster indicator of muscle metabolism, would be even more important for sports medicine than the nowadays‐used blood lactate.
Improving Gating Efficiency of Electron Transport through Redox‐Active Molecular Junctions with Conjugated Chains
Authors: Zhang Fan , Wu Xiao‐Hui , Zhou Yi‐Fan , Wang Ya‐Hao , Zhou Xiao‐Shun , Shao Yong , Li Jian‐Feng , Jin Shan , Zheng Ju‐Fang
Published: January 2020

Tuning the electron transport at the molecular scale is a key step in realizing functional electronic components for molecular electronics, and ongoing interest aims at achieving a higher modulation ratio for single‐molecular transistors. Here, a feasible strategy that connects the redox‐active moieties with conjugated chains is proposed to improve the electrochemical gating efficiency of molecular junctions in ionic liquid. Benefiting from the low energy barrier height between the Fermi level of the electrode and the frontier molecular orbitals, the conductance of C=C−Fc−Py is about one order of magnitude larger and the conductance on/off ratio shows 160 % improvement compared to that of C−C−Fc−Py at the equilibrium potential of Fc+/Fc. This work provides a new way to design high‐performance molecular devices.
One‐Pot Generation of Benzynes from Phenols: Formation of Primary Anilines by the Deoxyamination of Phenols
Authors: Ikawa Takashi , Masuda Shigeaki , Akai Shuji
Published: January 2020

Benzynes were selectively generated in situ from phenols and trapped regioselectively with potassium hexamethyldisilazide to form primary anilines following acidic workup. The direct conversion of a phenolic hydroxyl group into a free amino group is a useful method for the preparation of primary aryl amines that are hard to synthesize by using coupling reactions involving phenol derivatives with ammonia. Whereas reactions of ortho‐ and meta‐substituted phenols produced meta‐substituted anilines exclusively, those of para‐substituted phenols provided ortho‐silylanilines.
Theoretical Modeling of the Surface‐Guided Self‐Assembly of Functional Molecules
Authors: Nieckarz Damian , Szabelski Paweł
Published: January 2020

Directing the self‐assembly of organic building blocks with 2D templates has been a promising method to create molecular superstructures having unique physicochemical properties. In this work the on‐surface self‐assembly of simple ditopic functional molecules confined inside periodic nanotemplates was modeled by means of the lattice Monte Carlo simulation method. Two types of confinement, that is honeycomb porous networks and parallel grooves of controlled diameter and width were used in the calculations. Additionally, the effect of (pro)chirality of the adsorbing molecules on the outcome of the templated self‐assembly was examined. To that end, enantiopure and racemic assemblies were studied and the resulting structures were identified and classified. The obtained findings demonstrated that suitable tuning of the structural parameters of the templates enables directing the self‐assembly towards linear and cyclic aggregates with controlled size. Moreover, chiral resolution of the molecular conformers using honeycomb networks with adjusted pore size was found possible. Our theoretical predictions can be helpful in designing structured surfaces to direct self‐assembly and polymerization of organic functional building blocks.
Aza‐ortho‐Quinone Methide and Its Conjugated Acid: Reactivity, Stability and Acidity
Authors: Wu Tun‐Hui , Su Zih‐Syuan , Sung Robert , Sung Kuangsen
Published: January 2020

Aza‐o‐quinone methides and their conjugated acids are reactive drug metabolites that might react with nucleophilic sites of DNAs and proteins to cause cancer or immune responses, and their reactivity with water is the key information to judge if these metabolites are harmful in living systems. For the first time, aza‐o‐quinone methide (1) and its conjugated acid (2) are observed by laser flash photolysis, and their reactivity, stability and acidity in water are determined.
Oxidative Methane Conversion to Ethane on Highly Oxidized Pd/CeO2 Catalysts Below 400 °C
Authors: Kwon Gihun , Shin Dongjae , Jeong Hojin , Sahoo Suman Kalyan , Lee Jaeha , Kim Gunjoo , Choi Juhyuk , Kim Do Heui , Han Jeong Woo , Lee Hyunjoo
Published: January 2020

Methane upgrading into more valuable chemicals has received much attention. Herein, we report oxidative methane conversion to ethane using gaseous O2 at low temperatures (<400 °C) and atmospheric pressure in a continuous reactor. A highly oxidized Pd deposited on ceria could produce ethane with a productivity as high as 0.84 mmol gcat−1 h−1. The Pd−O−Pd sites, not Pd−O−Ce, were the active sites for the selective ethane production at low temperatures. Density functional theory calculations confirmed that the Pd−O−Pd site is energetically more advantageous for C−C coupling, whereas Pd−O−Ce promotes CH4 dehydrogenation. The ceria helped Pd maintain a highly oxidic state despite reductive CH4 flow. This work can provide new insight for methane upgrading into C2 species.
Continuous‐Flow Amide and Ester Reductions Using Neat Borane Dimethylsulfide Complex
Authors: Ötvös Sándor B. , Kappe C. Oliver
Published: January 2020

Reductions of amides and esters are of critical importance in synthetic chemistry, and there are numerous protocols for executing these transformations employing traditional batch conditions. Notably, strategies based on flow chemistry, especially for amide reductions, are much less explored. Herein, a simple process was developed in which neat borane dimethylsulfide complex (BH3⋅DMS) was used to reduce various esters and amides under continuous‐flow conditions. Taking advantage of the solvent‐free nature of the commercially available borane reagent, high substrate concentrations were realized, allowing outstanding productivity and a significant reduction in E‐factors. In addition, with carefully optimized short residence times, the corresponding alcohols and amines were obtained in high selectivity and high yields. The synthetic utility of the inexpensive and easily implemented flow protocol was further corroborated by multigram‐scale syntheses of pharmaceutically relevant products. Owing to its beneficial features, including low solvent and reducing agent consumption, high selectivity, simplicity, and inherent scalability, the present process demonstrates fewer environmental concerns than most typical batch reductions using metal hydrides as reducing agents.
Considering context in the developmental psychobiology of self‐regulation
Authors: Davis Elizabeth L. , Brooker Rebecca J. , Kahle Sarah
Published: January 2020

The developmental psychobiology of self‐regulation in childhood has received increasing attention in recent years. As a next step in advancing research and theorizing about the processes by which early biological correlates of self‐regulation are forged, a more nuanced consideration of the contexts in which these phenomena are embedded is needed. This review synthesizes insights from distinct but complementary approaches to studying the developmental psychobiology of early self‐regulation, focusing on the idea of context at different time scales. Three types of context that differ in temporal resolution are considered: (a) The temporally immediate contexts occurring within a structured challenge, including the baseline‐to‐task context of reactive psychobiology, the within‐task context of dynamic change, and the post‐task context of recovery from challenge. (b) The temporally moderate contexts of task type, including variants like the specific emotion that is under study and whether the task involves (or allows for) self‐regulatory behaviors. (c) The temporally chronic contexts of important social relationships within which children are embedded and developing. Future research efforts that incorporate a more nuanced appreciation for the temporal resolution of contexts in developmental psychobiology will allow for novel tests and refinement of theories of self‐regulation, as well as other domains of child development.
Butterfly phenology in Mediterranean mountains using space‐for‐time substitution
Authors: Zografou Konstantina , Grill Andrea , Wilson Robert J. , Halley John M. , Adamidis George C. , Kati Vassiliki
Published: January 2020

Inferring species' responses to climate change in the absence of long‐term time series data is a challenge, but can be achieved by substituting space for time. For example, thermal elevational gradients represent suitable proxies to study phenological responses to warming. We used butterfly data from two Mediterranean mountain areas to test whether mean dates of appearance of communities and individual species show a delay with increasing altitude, and an accompanying shortening in the duration of flight periods. We found a 14‐day delay in the mean date of appearance per kilometer increase in altitude for butterfly communities overall, and an average 23‐day shift for 26 selected species, alongside average summer temperature lapse rates of 3°C per km. At higher elevations, there was a shortening of the flight period for the community of 3 days/km, with an 8.8‐day average decline per km for individual species. Rates of phenological delay differed significantly between the two mountain ranges, although this did not seem to result from the respective temperature lapse rates. These results suggest that climate warming could lead to advanced and lengthened flight periods for Mediterranean mountain butterfly communities. However, although multivoltine species showed the expected response of delayed and shortened flight periods at higher elevations, univoltine species showed more pronounced delays in terms of species appearance. Hence, while projections of overall community responses to climate change may benefit from space‐for‐time substitutions, understanding species‐specific responses to local features of habitat and climate may be needed to accurately predict the effects of climate change on phenology.
Aerial spraying of bacterial insecticides to control spruce budworm defoliation leads to reduced carbon losses
Authors: Liu Zelin , Peng Changhui , De Grandpré Louis , Candau Jean‐Noël , Work Timothy , Zhou Xiaolu , Kneeshaw Daniel
Published: January 2020

Spruce budworm (SBW) outbreaks are a major natural disturbance in boreal forests of eastern North America. During large‐scale infestations, aerial spraying of bacterial insecticides is used to suppress local high‐density SBW populations. While the primary goal of spraying is the protection of wood volume for later harvest, it should also maintain carbon stored in trees. This study provides the first quantitative analysis of the efficacy of aerial spraying against SBW on carbon dynamics in balsam fir, spruce, and mixed fir–spruce forests. In this study, we used the TRIPLEX‐Insect model to simulate carbon dynamics with and without spray applications in 14 sites of the boreal forest located in various regions of Québec. We found that the efficacy of aerial spraying on reducing annual defoliation was greater in the early stage (<5 yr since the outbreak began) of the outbreak than in later (5–10 yr since the outbreak began) stage. Our results showed that more net ecosystem productivity is maintained in balsam fir (the most vulnerable species) than in either spruce or mixed fir–spruce forests following spraying. Also, average losses in aboveground biomass due to the SBW following spraying occurred more slowly than without spraying in balsam fir forests. Our findings suggest that aerial spraying could be used to maintain carbon in conifer forests during SBW disturbances, but that the efficacy of spray programs is affected by host species and stage of the SBW outbreak.
(Photo)Thermal Stimulation of Functional Dithiolene Complexes in Soft Matter
Authors: Camerel Franck , Fourmigué Marc
Published: January 2020

Square‐planar bis(dithiolene) complexes are characterized with a planar delocalized structure and a strong and tunable near infrared (NIR) absorption; they are highly stable under laser irradiation, and their conversion efficiency (light to heat) reaches up to 40–50 %. Their involvement in soft matter, namely liquid crystals, gels, and nanoparticles, opens many possibilities to control the actual state of a material, particularly under light irradiation. Thus, liquid crystalline phases can easily be modified, (i) with temperature to modulate the extended magnetic interactions of paramagnetic complexes, or (ii) under laser irradiation to unravel these remarkable photothermal properties, toward the development of light‐responsive materials. Dithiolene complexes can be also functionalized to produce very effective gelation agents, while the photothermal effect can be used to destabilize at will their supramolecular organization. Besides photothermal therapy, new therapeutic agents were also developed for photo‐controlled drug delivery and bioimaging, combining chemotherapy and phototherapy. Hydrophobic complexes were accordingly designed for their encapsulation in block copolymer nanoparticles for photothermal therapy and photo‐controlled drug delivery under laser irradiation. This class of complexes can be also used as exogenous contrast agents for photoacoustic bioimaging.
Activation of Water at the Active‐Site Cavity of Zinc Phthalocyanine with Tris(pentafluorophenyl)borane
Authors: Ikeuchi Takuro , Kudo Ryota , Yoshii Tatsuya , Kobayashi Nagao , Kitazawa Yu , Kimura Mutsumi
Published: January 2020

Activation of water bound with Zn2+ has attracted much attention as an artificial model of natural enzymes. Despite many attempts, water activation accompanied with a change in the coordination geometry of Zn2+ in complexes remains a challenge. In this study, we discover a new structure that is composed of partially protonated zinc phthalocyanine (ZnPc), hydroxide ion, and tris(pentafluorophenyl)borane (TPFB). The coordination of TPFB with water bounded with ZnPc results in the dissociation of water, and the dissociated proton from water moves to one nitrogen atom of the phthalocyanine ring through the intramolecular proton transfer. On the basis of this reaction, the coordination geometry transforms from a five‐coordinated to a distorted tetrahedral species. The Zn2+‐bound hydroxide nucleophile in the ZnPc‐TPFB complex attacks amide of ε‐caprolactam to produce hydrolyzed 6‐aminohexanoic acid in toluene.
The endo‐ and exo‐Anomeric Effects in Furanosides. A Computational Study
Authors: Gaweda Karolina , Plazinski Wojciech
Published: January 2020

The anomeric effect is rarely studied in the context of furanoses. Owing to large flexibility of the furanose ring, its influence is inherently coalesced with those of other steric and stereoelectronic factors governing the conformation and other molecular properties of furanoses. In this article the energetic magnitude of the exo‐ and endo‐anomeric effects in furanose systems is reported for the first time for a series of different ring substituents. Our computational study, performed at the M062X/6‐31G(d) level of theory, was complemented by the “hybrid” quantum mechanics/molecular mechanics–molecular dynamics simulations. The results indicate that the energetic magnitude of the endo‐anomeric effect changes in the following order of ring substituents: ‐Br > ‐Cl > ‐F > ‐OCH3 > ‐SCH3 > ‐OH > ‐NH2 > ‐CN > ‐CH3. The corresponding energies are highly correlated with the analogous values calculated for pyranoses, but are systematically larger by, on average, 2.7 kJ/mol. Analogously to pyranoses, the exo‐anomeric effect acts toward stabilization of the gauche+ or gauche‐rotamers for the axially‐ or equatorially‐oriented exocyclic, rotatable groups, respectively. However, the energy contributions to those rotamers differ between furanoses and pyranoses and are dependent on the substituent orientation.
Potassium Fluoride‐Catalyzed Hydroboration of Aldehydes and Ketones: Facile Reduction to Primary and Secondary Alcohols
Authors: Kuciński Krzysztof , Hreczycho Grzegorz
Published: January 2020

A catalytic hydroboration of various ketones and aldehydes can be achieved in the presence of inexpensive and commercially available inorganic salts containing fluoride anion. As a result, the reduction of carbonyl moieties to the corresponding primary and secondary alcohols can be achieved at room temperature under mild conditions.
A method to compute instantaneous oxygen evolution rates in cyanobacterial cultures grown in shake flasks
Authors: Sengupta Annesha , Wangikar Pramod P.
Published: January 2020

Cyanobacteria have been attracting attention for various biotechnological applications due to their ability to carry out oxygenic photosynthesis. The oxygen evolution rate (OER) of cyanobacterial cultures is a key physiological parameter, which is typically measured offline by using oxygen electrodes. In situ measurement of OER has been reported in a photobioreactor fitted with a dissolved oxygen (DO) probe. Here, we show that the OER can be estimated from online measurements of the DO levels by using sensors fitted in shake flasks, which are widely used for preliminary characterization of microbial strains. We study how the DO levels change under diurnal light regime and different growth conditions in two strains of Synechococcus elongatus, namely, PCC 7942 and PCC 11801, in shake flasks. We use the DO levels coupled with the knowledge of the overall gas‐liquid mass transfer coefficient for oxygen (kLa) to compute the OER. For the growth conditions tested, the cumulative oxygen evolved in a day correlated with the increase in biomass suggesting that the calculated OER, in turn, might provide an estimate of the organism's growth rate. We believe that the method may be widely applicable for the growth characterization of organisms that perform oxygenic photosynthesis.
Personality of late‐ and early‐onset elderly suicide attempters
Authors: Szücs Anna , Szanto Katalin , Wright Aidan G. C. , Dombrovski Alexandre Y.
Published: January 2020

Objectives

While suicidal behavior often manifests in adolescence and early adulthood, some people first attempt suicide in late life, often with remarkable lethal intent and determination. Given these individuals' more adaptive functioning earlier in life, they may possess traits that hinder adjustment to aging, such as high conscientiousness, rather than impulsive‐aggressive traits associated with suicidal behavior in younger adults.

Methods

A cross‐sectional case‐control study was conducted in older adults aged ≥50 (mean: 65), divided into early‐ and late‐onset attempters (age at first attempt ≤ or >50, mean: 31 vs 61), suicide ideators as well as non‐suicidal depressed and healthy controls. Personality was assessed in terms of the five‐factor model (FFM, n = 200) and five DSM personality disorders analyzed on the trait level as continuous scores (PDs, n = 160). Given our starting hypothesis about late‐onset attempters, the FFM dimension conscientiousness was further tested on the subcomponent level.

Results

All clinical groups displayed more maladaptive profiles than healthy subjects. Compared to depressed controls, higher neuroticism, and borderline traits characterized both suicide ideators and early‐onset attempters, while only early‐onset attempters further displayed lower extraversion and higher antisocial traits. Late‐onset attempters were similar to depressed controls on most measures, but scored higher than them on orderliness, a conscientiousness subcomponent.

Conclusions

While neuroticism, introversion, and cluster B traits are prominent in early‐onset suicidal behavior, late‐onset cases generally lack these features. In contrast, higher levels of orderliness in late‐onset suicidal behavior are compatible with the age‐selective maladjustment hypothesis.

Key points

Personality of elderly attempters differed between those with early‐ and late‐onset first attempts.

Early‐onset attempters possessed personality traits generally found in younger suicidal populations (high neuroticism, low extraversion, antisocial, and borderline PD traits), supporting that constitutional suicide risk factors persist into late life in some individuals.

Late‐onset suicide attempters had higher levels of orderliness than non‐suicidal depressed participants, suggesting that this generally adaptive trait may facilitate suicidal behavior in a subset of depressed elderly.
Prevalence of dementia in people with intellectual disabilities: Cross‐sectional study
Authors: Takenoshita Shintaro , Terada Seishi , Kuwano Ryozo , Inoue Tomokazu , Cyoju Atsushi , Suemitsu Shigeru , Yamada Norihito
Published: January 2020

Background

There are only a few studies of the prevalence of dementia in people with intellectual disability (ID) without Down syndrome (DS), and there is a large difference in the prevalences between reported studies. Moreover, the prevalence of mild cognitive impairment (MCI) in ID has not been reported. We aimed to evaluate the prevalence of dementia in adults of all ages and the prevalence of MCI in people with ID. Furthermore, we tried to clarify the differences depending on the various diagnostic criteria.

Methods

The survey included 493 adults with ID at 28 facilities in Japan. The caregivers answered a questionnaire, and physicians directly examined the participants who were suspected of cognitive decline. Dementia and MCI were diagnosed according to ICD‐10, DC‐LD, and DSM‐5 criteria.

Results

The prevalence of dementia was 0.8% for the 45 to 54 years old group, 3.5% for the 55 to 64 years old group, and 13.9% for the 65 to 74 years old group in people with ID without DS. The prevalence of MCI was 3.1% for patients 45 to 54, 3.5% for patients 55 to 64, and 2.8% for patients 65 to 74 with ID without DS. DSM‐5 was the most inclusive in diagnosing dementia and MCI in people with ID.

Conclusions

People with ID without DS may develop dementia and MCI at an earlier age and higher rate than the general population. Among the diagnostic criteria, DSM‐5 was the most useful for diagnosing their cognitive impairment.
Neuroticism predicts fear of falling after hip fracture
Authors: Bower Emily S. , Wetherell Julie L. , Petkus Andrew J. , Lenze Eric J.
Published: January 2020

Objectives

Fear of falling (FoF) is common and associated with poorer functional outcomes after hip fracture. We sought to differentiate patterns of FoF at 4 and 12 weeks after surgical repair for hip fracture and examine predictors of FoF.

Methods/design

Secondary analysis of existing data from a 52‐week prospective study examining recovery after hip fracture. Participants (N = 263) were aged 60 and older with recent hip fracture recruited from eight hospitals. FoF was measured 4 and 12 weeks postfracture with the Short Falls Efficacy Scale‐International. Latent class mixed models were constructed to identify distinct patterns of FoF from 4 to 12 weeks postfracture and predictors of FoF. Predictors examined included age, gender, neuroticism, depression, negative affect, perceived social support, medical comorbidity, functional ability, cognition, and pain.

Results

Three latent classes of FoF were identified: a group with minimal FoF at weeks 4 and 12 (72%), a group with high FoF that decreased (17%), and a group with high FoF that increased from week 4 to 12 (11%). In a multivariate model, higher neuroticism was associated with greater risk for high FoF (increasing or decreasing), whereas higher premorbid medical comorbidity was associated with increasing FoF, poorer premorbid functional ability was associated with decreasing FoF, and social support was not significantly associated.

Conclusions

Older adults with higher neuroticism are more likely to have FoF in the first 12 weeks after a hip fracture. Screening for neuroticism in health care settings might identify individuals who would benefit from interventions to improve outcomes during recovery.
Alcohol Use and Long‐Term Outcomes Among U.S. Veterans Who Received Direct‐Acting Antivirals for Hepatitis C Treatment
Authors: Kim Nicole J. , Pearson Meredith , Vutien Philip , Su Feng , Moon Andrew M. , Berry Kristin , Green Pamela K. , Williams Emily C. , Ioannou George N.
Published: January 2020

Outcomes related to alcohol use after hepatitis C virus (HCV) treatment are unknown in the direct‐acting antiviral (DAA) era. We assessed levels of alcohol use before and after HCV treatment and their association with long‐term outcomes in a cohort of U.S. veterans. In this retrospective cohort analysis, 29,037 patients who initiated DAA regimens between 2013 and 2015 were followed for a mean of 3.04 years. We categorized alcohol use into three categories (nondrinking, low‐level drinking, and unhealthy drinking) using Alcohol Use Disorders Identification Test‐Consumption questionnaires administered within 1 year before (baseline) and after treatment. Multivariable Cox proportional hazards regression was used to determine the associations between alcohol use and mortality or liver‐related outcomes. Before DAA treatment, 68% of veterans reported nondrinking, 22.9% reported low‐level drinking, and 9.1% reported unhealthy drinking. Compared to patients with baseline non‐drinking, those with unhealthy drinking had a higher risk of mortality (adjusted hazard ratio [HR] 1.53, 95% confidence interval [CI]: 1.34‐1.75) and decompensated cirrhosis (adjusted HR 1.30, 95% CI: 1.06‐1.59) and lower likelihood of liver transplantation (adjusted HR 0.24, 95% CI: 0.06‐0.92). These associations were greater in patients without sustained virologic response than in those with sustained virologic response. When alcohol use before and after treatment was modeled as a time‐varying covariate, similar associations were observed. Survival analysis also found that unhealthy drinking was significantly associated with a lower probability of survival compared with nondrinking. Low‐level alcohol use was not associated with increased risk of adverse outcomes. Conclusion: In this large cohort of U.S. veterans with HCV who received DAAs, unhealthy drinking was common and associated with a higher risk of posttreatment mortality. Interventions to achieve alcohol cessation before and during antiviral treatment should be encouraged.
Long‐term risk of colorectal cancer after screen‐detected adenoma: Experiences from a Danish gFOBT‐positive screening cohort
Authors: Bjerrum Andreas , Lindebjerg Jan , Andersen Ole , Fischer Anders , Lynge Elsebeth
Published: January 2020

Fecal occult blood test (FOBT) screening for colorectal cancer (CRC) is implemented in several countries. Approximately half of all FOBT‐positive persons have screen‐detected adenomas. Despite removal of these, patients with large/multiple adenomas have increased risk of later developing new advanced adenomas and CRC. International guidelines exist for colonoscopic surveillance following adenoma removal. These divide patients into low‐, intermediate‐ and high‐risk groups. We followed 711 FOBT‐positive patients with screening adenoma identified during population‐based CRC screening in two Danish counties in 2005–2006. As reference population, we included 1,240,348 persons in the same age group from the rest of Denmark not included in the screening. We estimated the long‐term CRC risk stratified by adenoma findings during screening and compared to the reference group. After 12 years follow‐up, the CRC incidence among all adenoma patients was 322 cases per 100,000 person‐years (95% confidence interval [CI]: 212–489) ranging from 251 (95% CI: 94–671) to 542 (95% CI: 300–978) cases per 100,000 person‐years in the low‐ and high‐risk groups, respectively. In the reference population, the CRC incidence was 244 (95% CI: 242–247) per 100,000. Patients with screen‐detected high‐risk adenomas after a positive FOBT had an almost doubled risk of CRC compared to the reference population (adjusted hazard ratio [aHR] 1.95, 95% CI: 1.08–3.51), and the incidence in those with no follow‐up visits was over 3.6 (aHR 3.64, 95% CI: 1.82–7.29) times the incidence in the reference population. The increased CRC risk could be controlled if high‐risk patients underwent follow‐up colonoscopy (aHR 0.87, 95% CI: 0.28–2.69).
Protective effect of hypoglycemic granule against diabetes‐induced liver injury by alleviating glycolipid metabolic disorder and oxidative stress
Authors: Yang Xiaosong , Zhang Pengjie , Zhang Feixue , Ke Zhiqiang , Chen Qingjie , Liu Chao
Published: January 2020

The current study was designed to explore the therapeutic effect and mechanism of different extraction, which came from hypoglycemic granule on diabetes‐induced liver injury. The ethanol fraction (HGEF) and aqueous fraction (HGAF) from hypoglycemic granule were prepared and administered p.o. to diabetic mice for 17 weeks after 6 weeks of constructing the model. Hematoxylin‐eosin (HE) staining and periodic acid‐Schiff (PAS) staining were individually applied to observe the morphological change and glycogen deposition. In addition, Oil Red O staining was adopted in lipid droplets detection. Western blot analysis was performed to evaluate the protein expression. The commercial biochemical kits were used to determine the fasting blood glucose value, enzyme activity, and some biochemical indicators. HGEF not only significantly decreased the levels of blood glucose, the content of triglycerides, total cholesterol, low‐density lipoprotein, and lipid droplet accumulation, but also remarkably enhanced the high‐density lipoprotein, glycogen synthesis, and further improved the hepatic function in diabetic mice. Moreover, HGEF increased the superoxide dismutase (SOD) activity and inhibited the malondialdehyde production, so did HGAF. HGAF performed potential to modulate lipid metabolism via decreasing TG and LDL levels. Further, the protein expressions of SOD, nuclear factor erythroid 2‐related factor 2 (Nrf2), and forkhead box O3 (Foxo3a) were increased by HGEF, whereas the receptor‐interacting serine‐threonine kinase 3 (RIP3), calcium/calmodulin‐dependent protein kinase II (CaMKII), and cytochrome c (Cyt c) expressions were inhibited. Our present results suggest that HGEF has superiority in ameliorating oxidative stress via modulating hepatic glycolipid metabolism homeostasis in low‐dose streptozotocin‐induced liver tissue of diabetic mice.
Use of Museum Specimens to Refine Historical Pronghorn Subspecies Boundaries
Authors: Hahn Erin E. , Klimova Anastasia , MUNGUÍA‐VEGA ADRIÁN , Clark Kevin B. , Culver Melanie
Published: January 2020

Endangered Sonoran (Antilocapra americana sonoriensis) and Peninsular (A. a. peninsularis) pronghorn persist largely because of captive breeding and reintroduction efforts. Recovery team managers want to re‐establish pronghorn in their native range, but there is currently uncertainty regarding the subspecies status of extinct pronghorn populations that historically inhabited southern California, USA, and northern Baja California, Mexico. To address this uncertainty, we genotyped museum specimens and conducted phylogenetic and population genetic analyses of historical data in the context of 3 contemporary pronghorn populations. The historical northern Baja California pronghorn share the most ancestry with contemporary Peninsular pronghorn, whereas pronghorn in southern California share more ancestry with contemporary American (A. a. americana) pronghorn. For reintroductions into northern Baja California, the Peninsular subspecies is more appropriate based on museum genetic data. For reintroductions into Southern California, ecological and genetic factors are both important, as the subspecies most genetically related to historical populations (American) may not be well‐adapted to the hot, low‐elevation deserts of the reintroduction area. © 2019 The Wildlife Society.