bluuebunny/crossref_metadata_2025 huggingface dataset:
Versatile Ferroelastic Deformability in an Organic Single Crystal by Twinning about a Molecular Zone Axis
Authors: Engel Emile R. , Takamizawa Satoshi
Published: May 2018

Ferroelasticity involves the generation of spontaneous strain in a solid by the application of mechanical stress. The phenomenon has been well‐studied in metal alloys but relatively neglected in organic solid‐state chemistry. Herein we present multiple discrete modes of mechanical twinning and a mechanistic analysis of ferroelasticity in 1,4‐diethoxybenzene. Single crystals of the compound can be almost freely deformed, as multiple different twin domains are generated simultaneously. Within each domain, single‐crystal character is preserved. Such extremely versatile, ferroelastic deformability is unprecedented in single crystals of any kind and defies the fragility and anisotropic mechanical behaviour of most organic crystals. The dissipated energy and critical stress associated with twinning deformation in 1,4‐diethoxybenzene suggests that organic solids could be developed for absorbing weak mechanical shocks in such applications as mechanical damping and soft robotics.
Alloying n‐Butylamine into CsPbBr3 To Give a Two‐Dimensional Bilayered Perovskite Ferroelectric Material
Authors: Wu Zhenyue , Ji Chengmin , Li Lina , Kong Jintao , Sun Zhihua , Zhao Sangen , Wang Sasa , Hong Maochun , Luo Junhua
Published: May 2018

Cesium‐lead halide perovskites (e.g. CsPbBr3) have gained attention because of their rich physical properties, but their bulk ferroelectricity remains unexplored. Herein, by alloying flexible organic cations into the cubic CsPbBr3, we design the first cesium‐based two‐dimensional (2D) perovskite ferroelectric material with both inorganic alkali metal and organic cations, (C4H9NH3)2CsPb2Br7 (1). Strikingly, 1 shows a high Curie temperature (Tc=412 K) above that of BaTiO3 (ca. 393 K) and notable spontaneous polarization (ca. 4.2 μC cm−2), triggered by not only the ordering of organic cations but also atomic displacement of inorganic Cs+ ions. To our knowledge, such a 2D bilayered Cs+‐based metal–halide perovskite ferroelectric material with inorganic and organic cations is unprecedented. 1 also shows photoelectric semiconducting behavior with large “on/off” ratios of photoconductivity (>103).
Chemoenzymatic Synthesis of Advanced Intermediates for Formal Total Syntheses of Tetrodotoxin
Authors: Baidilov Daler , Rycek Lukas , Trant John F. , Froese Jordan , Murphy Brennan , Hudlicky Tomas
Published: May 2018

Advanced intermediates for the syntheses of tetrodotoxin reported by the groups of Fukuyama, Alonso, and Sato were prepared. Key steps include the toluene dioxygenase mediated dihydroxylation of either iodobenzene or benzyl acetate. The resulting diene diols were transformed into Fukuyama's intermediate in six steps, into Alonso's intermediate in nine steps, and into Sato's intermediate in ten steps.
Direct Nanospectroscopic Verification of the Amyloid Aggregation Pathway
Authors: Lipiec Ewelina , Perez‐Guaita David , Kaderli Janina , Wood Bayden R. , Zenobi Renato
Published: May 2018

The aggregation pathways of neurodegenerative peptides determine the disease etiology, and their better understanding can lead to strategies for early disease treatment. Previous research has allowed modelling of hypothetic aggregation pathways. However, their direct experimental observation has been elusive owing to methodological limitations. Herein, we demonstrate that nanoscale chemical mapping by tip‐enhanced Raman spectroscopy of single amyloid fibrils at various stages of aggregation captures the fibril formation process. We identify changes in TERS/Raman marker bands for Aβ1‐42, including the amide III band (above 1255 cm−1 for turns/random coil and below 1255 cm−1 for β‐sheet conformation). The spatial distribution of β‐sheets in aggregates is determined, allowing verification of a particular fibrillogenesis pathway, starting from aggregation of monomers to meta‐stable oligomers, which then rearrange to ordered β‐sheets, already at the oligomeric or protofibrillar stage.
Chemical Characterization of a High‐Oleic Soybean Oil
Authors: Napolitano Guillermo E. , Ye Yubin , Cruz‐Hernandez Cristina
Published: May 2018

High‐oleic low‐linolenic acid soybean oil (HOLLSB, Plenish®) is an emerging new oil with projections of rapid expansion in the USA. HOLLSB has important technological advantages, which are expected to drive a gradual replacement of commodity oils used in food applications such as soybean oil. A key technological advantage of HOLLSB is its relatively high oxidation stability. This oxidation stability is the result of a favorable fatty acid composition, high (76%) oleic acid, low linoleic (6.7%), and alpha‐linolenic (1.6%) acids, and high concentration of tocopherols (936 ppm) after refining, enriched with the gamma‐homolog (586 ppm). A detailed analysis of the fatty acid composition of this HOLLSB by gas chromatography–mass spectrometry allowed the identification and structural determination of 9‐cis‐heptadecenoic acid (or 17:1n‐8). To our knowledge, this is the first time 9‐cis‐heptadecenoic acid has been unequivocally reported in soybean oil. This unusual fatty acid component has the potential to be used as a single authenticity marker for the quantitative assessment of soybean oil. The Rancimat induction period (IP) of Plenish® (16.1 hours) was higher than those of other commercially available high‐oleic oils, such as canola (13.4 hours), and Vistive® Gold (10 hours), a different variety of soybean oil. Plenish® showed the same IP as high‐oleic sunflower oil. Plenish® shows a modest increase in oxidation stability with the external addition or relatively high concentrations of tocopherols. The characteristic high oxidative stability of Plenish® may be further enhanced with the use of nontocopherol antioxidants.
Investigation on elemental mercury removal and antideactivation performance of modified SCR catalysts
Authors: Lv Qiang , Cai Ming , Wang Chang'an , Zhang Zehan , Che Defu
Published: May 2018

The ever‐growing concern of mercury exhausted from coal‐fired boiler is driving the requirement for using novel catalysts with stable Hg0 removal efficiency. However, the influences of flue gas components on Hg0 removal performance of modified and deactivated catalysts have been seldom investigated previously. The antideactivation ability of modified catalysts is still unclear. In this study, cerium (Ce) and zirconium (Zr) were utilized to modify the honeycomb V2O5–WO3/TiO2 catalysts. Sodium (Na) was doped on the rudimentary and modified catalysts by impregnation method to obtain deactivated catalysts. Elemental mercury removal efficiency of the catalysts was measured using a lab‐scale experimental system under various working conditions. Characterization of the catalysts was conducted to further analyze the mechanism of Hg0 removal process. Physical adsorption plays an important role in Hg0 removal over catalysts in the atmosphere of N2 and O2. The introduction of SO2 has an adverse effect on Hg0 removal because of the competitive adsorption. NO and HCl motivate the Hg0 removal through different mechanisms whereas NH3 has little effect on the removal efficiency. Mars–Maessen mode could be responsible for the excellent Hg0 removal performance and the splendid antideactivation ability of Ce‐modified catalysts. The efficiency of Zr‐modified catalysts is lower due to the decline of vanadium content.
Matchmaking: Establishment of state‐owned holding companies in Indonesia
Authors: Kim Kyunghoon
Published: May 2018

Under the government of President Joko Widodo, Indonesia's state‐owned enterprises (SOEs) have become the driver of the national development strategy. The current administration is actively using SOEs to conduct development projects based on the belief that SOEs are able to fix market failures and support the fiscally constrained government. In order to strengthen the role of SOEs, the Indonesian government is pursuing a medium‐term plan of creating sector‐based holding companies. The government expects that these state‐owned holding companies (SOHCs) will enable SOEs to expand investment and benefit from synergies. However, considering political hurdles in implementing this policy, the process of establishing SOHCs is expected to advance gradually. The government also continues to face challenges clarifying and communicating the rationale behind creating SOHCs. This paper examines the current political economic context of SOE ownership reorganisation in Indonesia and diverse views on the expected consequences of forming SOHCs.
Brief Report: Anti–Calponin 3 Autoantibodies: A Newly Identified Specificity in Patients With Sjögren’s Syndrome
Authors: Birnbaum Julius , Hoke Ahmet , Lalji Aliya , Calabresi Peter , Bhargava Pavan , Casciola‐Rosen Livia
Published: May 2018

Objective

Autoantibodies are clinically useful for phenotyping patients across the spectrum of autoimmune rheumatic diseases. Using serum from a patient with Sjögren's syndrome (SS), we detected a new specificity by immunoblotting. This study was undertaken to identify this autoantibody and to evaluate its disease specificity.

Methods

A prominent 40‐kd band was detected when immunoblotting was performed using SS patient serum and lysate from rat dorsal root ganglia (DRGs). Using 2‐dimensional gel electrophoresis and liquid chromatography tandem mass spectrometry peptide sequencing, the autoantigen was identified as calponin 3. Anti–calponin 3 antibodies were evaluated in sera from patients with primary SS (n = 209), patients with systemic lupus erythematosus (SLE; n = 138), patients with myositis (n = 138), patients with multiple sclerosis (MS; n = 44), and healthy controls (n = 46) by enzyme‐linked immunosorbent assay. Expression of calponin 3 was assessed by immunohistochemistry.

Results

Calponin 3 was identified as a new autoantigen. Anti–calponin 3 antibodies were detected in 23 (11.0%) of the 209 SS patients, 12 (8.7%) of the 138 SLE patients, 7 (5.1%) of the 138 myositis patients, 3 (6.8%) of the 44 MS patients, and 1 (2.2%) of the 46 healthy controls. Among SS patients, the frequency of anti–calponin 3 antibodies was highest in those with neuropathies (7 [17.9%] of 39). In this subset, the frequency of anti–calponin 3 antibodies differed significantly from that in the control group (P = 0.02). Calponin 3 was expressed primarily in rat DRG perineuronal satellite cells but not neurons.

Conclusion

Calponin 3 is a novel autoantigen. Antibodies against this protein are found in SS and associate with the subset of patients experiencing neuropathies. Intriguingly, we found that calponin 3 is expressed in DRG perineuronal satellite cells, suggesting that these may be a target in SS.
Marginalized zero‐inflated Poisson models with missing covariates
Authors: Benecha Habtamu K. , Preisser John S. , Divaris Kimon , Herring Amy H. , Das Kalyan
Published: May 2018

Unlike zero‐inflated Poisson regression, marginalized zero‐inflated Poisson (MZIP) models for counts with excess zeros provide estimates with direct interpretations for the overall effects of covariates on the marginal mean. In the presence of missing covariates, MZIP and many other count data models are ordinarily fitted using complete case analysis methods due to lack of appropriate statistical methods and software. This article presents an estimation method for MZIP models with missing covariates. The method, which is applicable to other missing data problems, is illustrated and compared with complete case analysis by using simulations and dental data on the caries preventive effects of a school‐based fluoride mouthrinse program.
Building a genome engineering toolbox in nonmodel prokaryotic microbes
Authors: Freed Emily , Fenster Jacob , Smolinski Sharon L. , Walker Julie , Henard Calvin A. , Gill Ryan , Eckert Carrie A.
Published: May 2018

The realization of a sustainable bioeconomy requires our ability to understand and engineer complex design principles for the development of platform organisms capable of efficient conversion of cheap and sustainable feedstocks (e.g., sunlight, CO2, and nonfood biomass) into biofuels and bioproducts at sufficient titers and costs. For model microbes, such as Escherichia coli, advances in DNA reading and writing technologies are driving the adoption of new paradigms for engineering biological systems. Unfortunately, microbes with properties of interest for the utilization of cheap and renewable feedstocks, such as photosynthesis, autotrophic growth, and cellulose degradation, have very few, if any, genetic tools for metabolic engineering. Therefore, it is important to develop “design rules” for building a genetic toolbox for novel microbes. Here, we present an overview of our current understanding of these rules for the genetic manipulation of prokaryotic microbes and the available genetic tools to expand our ability to genetically engineer nonmodel systems.
Simultaneous Determination and Stability Test of Two Phthalic Anhydride Derivatives, Senkyunolide A and Z‐Ligustilide, in the Water Extract of Cnidium Rhizome from Different Geographical Regions and Species Using HPLC‐UVD Analysis
Authors: Jang Hyeon Seok , Kang Kyo Bin , Yoo Guijae , Kwon Euna , Yun Jun‐Won , Kang Byeong‐Cheol , Hong In Kee , Kim Seung Hyun , Sung Sang Hyun , Cho Hyun‐Jong , Jang Young Pyo , Yang Heejung
Published: May 2018

Cnidium rhizome from Cnidium officinale Makino and Ligusticum chuanxiong Hort (Umbelliferae) is traditionally used to treat pain in East Asian countries. Senkyunolide A and Z‐ligustilide are phthalic anhydride derivatives that are the bioactive components of cnidium rhizome and chemical markers of the two species; they are also susceptible to external stimuli. In this study, we developed a method to identify two chemical markers using high‐performance liquid chromatography (HPLC) with an ultraviolet detector (UVD); the contents of senkyunolide A and Z‐ligustilide in cnidium rhizome from different regions were quantified. The stabilities of the compounds were tested at two different temperatures over 12 months. An HPLC‐UVD system was used to identify and quantify senkyunolide A and Z‐ligustilide in 10 C. officinale samples and 6 L. chuanxiong samples from China and Korea. The long‐term stability of the C. officinale samples in dark conditions at 4 and 25 °C was also tested. The calibration curves for the two chemical markers showed high linearity (R2 = 1.0000), the precision was high (relative standard deviation (RSD) <4.17%), and the recoveries were within the range of 95–105%. The contents were mostly independent of the geographical origin and species, and >10% of the compounds degraded after storage at 4 and 25 °C for 6 months. A method was developed to rapidly identify two chemical markers in cnidium rhizome with good linearity, precision, and accuracy using HPLC‐UVD. These markers will be utilized for the quality control or evaluation of herbal preparations containing cnidium rhizome.
Changes in intestinal microbiota affect metabolism of ginsenoside Re
Authors: Zhang Lei , Li Fei , Qin Wang‐Jun , Fu Chao , Zhang Xiang‐Lin
Published: May 2018

Ginsenoside Re, an active ingredient in Panax ginseng, is widely used as a therapeutic and nutriment. The intestinal microbiota plays crucial roles in modulating the pharmacokinetics and pharmacological actions of ginsenoside Re. The aim of this study was to explore the relationship between bacterial community variety and the metabolic profiles of ginsenoside Re. We developed two models with intestinal dysbacteriosis: a pseudo‐germ‐free model induced by a nonabsorbable antimicrobial mixture (ATM), and Qi‐deficiency model established via over‐fatigue and acute cold stress (OACS). First, the bacterial community structures in control, ATM and OACS rats were compared via 16S ribosomal RNA amplicon sequencing. Then, the gut microbial metabolism of ginsenoside Re was assessed qualitatively and quantitatively in the three groups by UPLC‐Q‐TOF/MS and HPLC‐TQ‐MS, respectively. Ten metabolites of ginsenoside Re were detected and tentatively identified, three of which were novel. Moreover, owing to significant differences in bacterial communities, deglycosylated products, as the main metabolites of ginsenoside Re, were produced at lower levels in ATM and OACS models. Importantly, the levels of these deglycosylated metabolites correlated with alterations in Prevotella, Lactobacillus and Bacteroides populations, as well as glycosidase activities. Collectively, biotransformation of ginsenoside Re is potentially influenced by regulation of the composition of intestinal microbiota and glycosidase activities.
Clinical considerations for implementing exposure and response prevention for pediatric OCD
Authors: Herren Jenny , Brannan Elizabeth
Published: May 2018

Obsessive‐compulsive disorder (OCD) is a neurobehavioral disorder that impacts individuals across the lifespan. Cognitive behavioral therapy using exposure with response prevention (E/RP) has been identified as the first‐line and “gold standard” treatment for OCD and has been well‐studied in children and adolescents (Freeman et al., 2014). Exposure‐based treatment involves an individual purposefully facing anxiety‐provoking stimuli while refraining from engaging in rituals or avoidance. Research studies with youth (ages 8–17) and younger patients (under 8) have identified individual and family‐based E/RP to be an efficacious, well‐tolerated, and acceptable treatment for OCD (Freeman et al., 2014). Delivering exposure in a developmentally sensitive manner for youth is important to facilitate optimal treatment response. This article focuses on a few key considerations when using E/RP with a pediatric population. To exemplify the principles, we will give examples of E/RP with a 10‐year‐old female (“Julia”) presenting with a primary fear of contamination through toxic chemicals. Rituals involve checking, cleaning, reassurance seeking, counting, and avoidance measures.
Keep your eye on…
Authors: Knopf Alison
Published: May 2018

SAMHSA chief's warning: Marijuana is not a ‘healthy pastime’

Vaping as a gateway to marijuana

The rising costs due to NAS of Medicaid births
Autism rates increase slightly: CDC
Authors: Knopf Alison
Published: May 2018

The rates of autism in school‐aged children have increased slightly, from one in 68 children (1.5%) to one in 59 (1.7%), according to the federal Centers for Disease Control and Prevention (CDC). Published in the CDC's April 27 Morbidity and Mortality Weekly Report, the study of autism spectrum disorder (ASD) during 2014 is based on the Autism and Developmental Disabilities Monitoring (ADDM) Network, an active surveillance system. It provides estimates of the prevalence of ASD among children aged 8 years whose parents or guardians reside within Arizona, Arkansas, Colorado, Georgia, Maryland, Minnesota, Missouri, New Jersey, North Carolina, Tennessee and Wisconsin — the ADDM sites.
Violence in schools: Our failure to protect children
Authors: Walters Anne
Published: May 2018

“Since 2014 there have been an average of 5 school shootings per month. Since Sandy Hook in 2012, there have been at least 239 school shootings nationwide. In these episodes, 438 were shot and 138 were killed, and 16 can be classified as events where 4 or more people were shot” (New York Times, 2/15/2018, data taken from the Gun Violence Archive).
Spanking doesn't work and is counterproductive
Authors: Knopf Alison
Published: May 2018

Rather than making behavior better, spanking makes it worse, with children more likely to be defiant and more likely to have increased antisocial behavior, aggression, and cognitive difficulties, research published last year in the Journal of Family Psychology found. The study looked at 50 years of research involving more than 160,000 children.
Sputtered Titanium Nitride Films on Titanium Foam Substrates as Electrodes for High‐Power Electrochemical Capacitors
Authors: Zheng Tianye , Tahmasebi Mohammad H. , Li Bei , Li Ying , Ran Sijia , Glen Tom S. , Lam Kwok‐Ho , Choi In‐Suk , Boles Steven T.
Published: May 2018

Electrochemical capacitors (ECs) with high‐power capabilities and stable cycling can effectively improve the state of the art in power delivery and energy storage. In this study, we investigate reactively sputtered titanium nitride (TiN) electrodes on three‐dimensional (3D) substrates with various electrolytes and high‐rate cycling conditions. The electrode exhibits cycling stability with negligible capacitance fading after 5 000 cycles and a great rate capability, allowing the (dis)charge rate to extend from 0.1 to 10 V s−1 and retaining nearly 50 % of the capacitance in a three‐electrode system. A symmetric device made with such electrodes is capable of working at a scan rate up to 100 V s−1, yielding a remarkable power density of 4.81×105 W kg−1 at 1.60 Wh kg−1. The energy density can be pushed to 168.03 Wh kg−1 at 4.03×104 W kg−1 by replacing the aqueous electrolyte with an organic one, and this can likely be further increased by electrolyte optimization. The material synthesis and device processing suggest that 3D TiN structures can enable a new class of high‐power ECs with enhanced stability compared to their carbon‐ and pseudo‐ counterparts.
Biocatalytic Production of Psilocybin and Derivatives in Tryptophan Synthase‐Enhanced Reactions
Authors: Blei Felix , Baldeweg Florian , Fricke Janis , Hoffmeister Dirk
Published: May 2018

Psilocybin (4‐phosphoryloxy‐N,N‐dimethyltryptamine) is the main alkaloid of the fungal genus Psilocybe, the so‐called “magic mushrooms.” The pharmaceutical interest in this psychotropic natural product as a future medication to treat depression and anxiety is strongly re‐emerging. Here, we present an enhanced enzymatic route of psilocybin production by adding TrpB, the tryptophan synthase of the mushroom Psilocybe cubensis, to the reaction. We capitalized on its substrate flexibility and show psilocybin formation from 4‐hydroxyindole and l‐serine, which are less cost‐intensive substrates, compared to the previous method. Furthermore, we show enzymatic production of 7‐phosphoryloxytryptamine (isonorbaeocystin), a non‐natural congener of the Psilocybe alkaloid norbaeocystin (4‐phosphoryloxytryptamine), and of serotonin (5‐hydroxytryptamine) by means of the same in vitro approach.
Visible‐Light Catalytic Photooxygenation of Monoterpene Indole Alkaloids: Access to Spirooxindole‐1,3‐oxazines
Authors: von Drathen Thorsten , Hoffmann Frank , Brasholz Malte
Published: May 2018

Few natural oxindole alkaloids possess an exceptional spiro‐[(1,3)oxazinan‐3,6′‐oxindole] core structure, which results from an unusual oxidative indole rearrangement. The Rauvolfia alkaloid reserpine can be converted into the spirooxindole‐1,3‐oxazines dioxyreserpine and trioxyreserpine through efficient visible‐light catalytic photooxygenation with anthraquinone photocatalysts. A mechanistic investigation sheds new light on the photooxidative rearrangement of reserpine and related monoterpene indole alkaloids, and the spirooxindole‐1,3‐oxazine products can be valorized by reductive ring opening, to obtain cis‐decahydroisoquinolines as new enantiopure synthetic building blocks, as demonstrated for dioxyreserpine.
Nickel‐Catalyzed Coupling of Arylzinc Halides with Thioesters
Authors: Gehrtz Paul H. , Kathe Prasad , Fleischer Ivana
Published: May 2018

The Pd‐catalyzed Fukuyama reaction of thioesters with organozinc reagents is a mild, functional‐group‐tolerant method for acylation chemistry. Its Ni‐catalyzed variant might be a sustainable alternative to expensive catalytic Pd sources. We investigated the reaction of S‐ethyl thioesters with aryl zinc halides with hetero‐ and homotopic Ni precatalysts and several ligands. The results show that both homo‐ and heterotopic species may contribute to catalysis. The substrate scope using an operationally homogeneous defined Ni complex was established. Acyl radicals are postulated as short‐lived intermediates.
Understanding Patient Adherence and Concerns with STatins and MedicatION Discussions With Physicians (ACTION): A survey on the patient perspective of dialogue with healthcare providers regarding statin therapy
Authors: Brinton Eliot A.
Published: May 2018

Background

Statins are first‐line for cholesterol lowering and prevention of atherosclerotic cardiovascular disease (ASCVD), but their use is complicated by side effects and potential for drug–drug interactions. Provider‐patient communication is the basis of the recommended shared decision‐making, but relatively little is known about this in the context of statin use.

Methods

We surveyed 5014 US adults prescribed a statin for hypercholesterolemia to learn their perspectives on communication with their provider.

Results

Ninety‐four percent reported currently taking a statin while 6% had stopped. Past users vs current users were more likely to be female, age < 65 years, and to have fewer cardiovascular disease–related comorbidities (hypertension, type 2 diabetes mellitus, and coronary heart disease, respectively). Although 93% of current statin users were taking ≥1 other prescription medications (median of 4), 76% were “not at all”/“not very concerned” about potential drug–drug interactions with their statin, and fewer than one‐quarter recalled mention of these from their provider. Ninety‐five percent of subjects said it was “extremely”/“somewhat” important that their healthcare provider take “an individualized approach to selecting the right statin,” but 73% and 76%, respectively, said their statin choice was made with little or no input from them. Only 25% were told that “some statins might be more likely than others to interact with other medications,” and only 18% (and only 20% of past users) were told that “their particular statin might interact with other medications.”

Conclusion

Provider‐patient communication regarding statin therapy appears inadequate, by patient recall, and efforts to improve it are warranted.
Modeling the Accumulation of Degradable Polymer Drug Carriers in the Brain
Authors: Bolwerk Celine , Govers Larissa P. M. W. D. , Knol Hanna , Oostendorp Thom F. , Brock Roland
Published: May 2018

The blood–brain barrier (BBB) limits the access of drugs to the brain. Intensive research is being conducted on the development of nanoparticulate drug carriers that mediate transfer across the BBB. A question that has been neglected so far is the potential accumulation of the carrier in the brain upon long‐term exposure. Here, we address this question by implementing a kinetic model to relate drug loading, required concentration of drug in the brain, and drug clearance to the degradation half‐life of the carrier. As a test case with clinical relevance we chose poly‐lactic‐co‐glycolic‐acid (PLGA) as a carrier material and a chemotherapeutic for which the required parameters could be recovered from the literature. For methotrexate with a drug load of 8.5 %, a required concentration of free drug of 1 μm, a release from PLGA of 6 hours, a drug clearance from the brain of 3 hours and a half‐life of polymer degradation of 28 days, a steady‐state accumulation of 1.3 g polymer would be reached in the brain (1.5 L) after seven months. While this number is surprisingly small, further physiological research is warranted to assess to which degree this will be in a tolerable range.
Comparative Randomized, Single‐Dose, Two‐Way Crossover Open‐Label Study to Determine the Bioequivalence of Two Formulations of Dalfampridine Tablets
Authors: Al Bawab Abdel Qader , Alkhalidi Bashar A. , Albarahmieh Esra'a , Qassim Sami M.A. , Al‐Saifi Mohammad A. D.
Published: May 2018

Dalfampridine is a medication that is approved by the US Food and Drug Administration to improve walking impairments in patients with multiple sclerosis (MS). The branded dalfampridine is enormously expensive; hence, the availability of generic dalfampridine will provide better access to the medication, especially for uninsured patients with MS. Bioequivalence studies are demanded by the regulatory authorities to allow the marketing of new generics of dalfampridine. The aim of this study was to assess the bioavailability of the generic (test) and branded (reference) formulations of 10 mg dalfampridine of extended‐release tablets after oral administration to healthy adults under fed conditions. The current report methodology was based on a comparative, randomized, single‐dose, 2‐way crossover open‐label study design. Twenty‐seven subjects were given a single dose of the test dalfampridine tablet and completed the clinical study. The pharmacokinetic parameters Cmax and AUC0→t, Kel, AUC0→∞, tmax, and t1/2el were estimated to prove bioequivalence. The confidence intervals for the log‐transformed test/reference ratios for dalfampridine 100.96% (97.09%–104.97%) and 99.77% (95.81%–103.87%) for Cmax and AUC0→∞, respectively, were within the allowed limit specified by the regulatory authorities (80%–125%). Hence, clinically, the test tablet can be prescribed as an alternative to the reference for the indication of improving walking impairments in patients with MS.
Atomic Force Microscopy Study of the Influence of the Synthesis Conditions on the Single‐Crystal Surface of Interdigitated Metal‐Organic Frameworks
Authors: Kamakura Yoshinobu , Hosono Nobuhiko , Terashima Aya , Kitagawa Susumu , Yoshikawa Hirofumi , Tanaka Daisuke
Published: May 2018

Metal–organic frameworks (MOFs) containing two or more types of metal ions exhibit promising new functionalities. To precisely control the distribution of metal ions, the relationship between the crystal‐growth mechanism and the metal‐ion type is important. Therefore, we investigated this relationship by using atomic force microscopy (AFM), which provided significant information about crystal‐growth processes. We focus on interdigitated MOFs of the type: {[M(ip)(bpy)]⋅solvent}n (M=Zn or Cd, ip=isophthalate, bpy=4,4′‐bipyridine, solvent=water or N,N‐dimethylformamide). AFM images show two surface condition types that strongly depend on the solvent or synthetic conditions. We also demonstrate that the adsorption properties between different crystal surfaces are affected by the surface conditions. Finally, we synthesize solid‐solution MOFs and observe their surface conditions. Such mechanistic insights will aid in the design of the adsorption properties of multi‐metal MOFs.
Hierarchical NiCoO2 Nanosheets Anchored on Hollow Carbon Spheres for High‐Performance Lithium‐Ion Battery Anodes
Authors: Chen Sheng , Liang Jin , Pang Yuanchao , Dong Bitao , Xu Xin , Ding Shujiang
Published: May 2018

This study reports the synthesis of hierarchical NiCoO2 nanosheets growing on hollow carbon spheres (denoted as NiCoO2 NSs@HCS) via a facile and low‐cost process. When evaluated as anode materials for lithium‐ion batteries, the as‐prepared NiCoO2 NSs@HCS exhibits high specific capacity, enhanced cycling stability, and good rate capability. A high discharge capacity of 631.7 mA h g−1 is delivered even after 200 cycles at a current density of 400 mA g−1, corresponding to approximately 92 % of the second reversible discharge capacity. The hierarchical and hollow structure of NiCoO2 NSs@HCS plays a role in its excellent performance.
Lipase‐Catalyzed Synthesis of Furan‐Based Oligoesters and their Self‐Assembly‐Assisted Polymerization
Authors: Muthusamy Kumarasamy , Lalitha Krishnamoorthy , Prasad Yadavali Siva , Thamizhanban Ayyapillai , Sridharan Vellaisamy , Maheswari C. Uma , Nagarajan Subbiah
Published: May 2018

We investigate the synthesis of bio‐based hydrophilic and hydrophobic oligoesters, which in turn are derived from easily accessible monomers from natural resources. In addition to the selection of renewable monomers, Novozyme 435, an immobilized lipase B from Candida antarctica was used for the oligomerization of monomers. The reaction conditions for oligomerization using Novozyme 435 were established to obtain a moderate‐to‐good yield. The average number of repeating units and the molecular weight distribution of hydrophilic and hydrophobic oligoester were identified by using NMR spectroscopy, gel‐permeation chromatography, and MS. The oligoester derived from a hydrophilic monomer self‐assembled to form a viscous solution, which upon further heating resulted in the formation of a polymer by the intermolecular Diels–Alder reaction. The viscosity of the solution and the assembly of oligoester to form a fibrous structure were investigated by using rheological studies, XRD, and SEM. The molecular weight of the cross‐linked polymer was identified by using matrix‐assisted laser desorption/ionization–MS. The thermal properties of the bio‐based polymers were investigated by using thermogravimetric analysis and differential scanning calorimetry. For the first time, the self‐assembly‐assisted polymerization of an oligoester is reported using the intermolecular Diels–Alder reaction, which opens a new avenue in the field of polymer science.
Design of a Mesoscale Continuous‐Flow Route toward Lithiated Methoxyallene
Authors: Seghers Sofie , Heugebaert Thomas S. A. , Moens Matthias , Sonck Jolien , Thybaut Joris W. , Stevens Christian V.
Published: May 2018

The unique nucleophilic properties of lithiated methoxyallene allow for C−C bond formation with a wide variety of electrophiles, thus introducing an allenic group for further functionalization. This approach has yielded a tremendously broad range of (hetero)cyclic scaffolds, including precursors to active pharmaceutical ingredients. To date, however, its valorization at scale is hampered by the batch synthesis procedure, which suffers from serious safety issues. Hence, the attractive heat‐ and mass‐transfer properties of flow technology were exploited to establish a mesoscale continuous‐flow route toward lithiated methoxyallene. An excellent conversion of 94 % was obtained, corresponding to a methoxyallene throughput of 8.2 g h−1. The process is characterized by short reaction times, mild reaction conditions and a stoichiometric use of reagents.
Physiological linkage and affective dynamics in dyadic interactions between adolescents and their mothers
Authors: McKillop Hannah N. , Connell Arin M.
Published: May 2018

This study examined physiological linkage (specifically, linkage in respiratory sinus arrhythmia; RSA) between parents and youth (aged 11–17) across conflict and fun activity discussion tasks. We also examined whether observed, momentary negative affect or parental depressive symptoms, would moderate patterns of RSA linkage across the interaction tasks. RSA linkage was assessed using a multilevel actor–partner interdependence model (APIM). Participants were 59 mother–adolescent dyads, including mothers with or without clinically significant depressive symptoms. Both mothers and teens evidenced stable RSA over time (actor effect), although the stability of maternal RSA was moderated by maternal depression, with maternal depressive symptoms related to slower RSA return to baseline. There was a significant partner influence on youth RSA, with maternal RSA positively related to subsequent youth RSA. However, this effect was moderated by maternal depression and maternal negative affect (NA), with low maternal depression/low maternal NA related to dyadic synchrony, whereas high depression or high NA led to attenuation of this relationship. Results demonstrate the importance of understanding the dynamic and complex nature of family interactions in the context of depression.
Neonatal pain and stress disrupts later‐life pavlovian fear conditioning and sensory function in rats: Evidence for a two‐hit model
Authors: Davis Seth M. , Rice Makaela , Rudlong Jacob , Eaton Victoria , King Tamara , Burman Michael A.
Published: May 2018

Early life trauma has been linked to increased risks for anxiety, depression, and chronic pain. We used rodent models of acute and inflammatory neonatal pain to explore effects on fear conditioning and somatosensory function. Hindpaw needle pricks or handling on postnatal days (PNDs) 1–7 caused lasting impacts on affective and somatosensory function when assessed at later ages, PNDs 24 (postweaning), 45 (adolescence), or 66 (adulthood). First, auditory, but not contextual, freezing was mildly disrupted regardless of age. Second, a profound postfear conditioning tactile hypersensitivity was observed in neonatally stressed, postweaning rats. In the absence of fear conditioning, the mechanical hypersensitivity was not observed, consistent with a two‐hit model of psychopathology. Injections of 2% α‐carrageenan did not have the same lasting impact but was slightly protective against observed effects of neonatal vehicle injections. Basal and elicited corticosterone levels postweaning were not altered by neonatal pain or handling. These data demonstrate that neonatal adversity can have lasting impacts on affective and somatosensory function that differs regardless of age.
Systematic optimisation of ethyl glucuronide extraction conditions from scalp hair by design of experiments and its potential effect on cut‐off values appraisal
Authors: Alladio Eugenio , Biosa Giulia , Seganti Fabrizio , Di Corcia Daniele , Salomone Alberto , Vincenti Marco , Baumgartner Markus R.
Published: May 2018

The quantitative determination of ethyl glucuronide (EtG) in hair samples is consistently used throughout the world to assess chronic excessive alcohol consumption. For administrative and legal purposes, the analytical results are compared with cut‐off values recognised by regulatory authorities and scientific societies. However, it has been recently recognised that the analytical results depend on the hair sample pretreatment procedures, including the crumbling and extraction conditions. A systematic evaluation of the EtG extraction conditions from pulverised scalp hair was conducted by Design of Experiments (DoE) considering the extraction time, temperature, pH, and solvent composition as potential influencing factors. It was concluded that an overnight extraction at 60°C with pure water at neutral pH represents the most effective conditions to achieve high extraction yields. The absence of differential degradation of the internal standard (isotopically‐labelled EtG) under such conditions was confirmed and the overall analytical method was validated according to SGWTOX and ISO17025 criteria. Twenty real hair samples with different EtG content were analysed with 3 commonly accepted procedures: (a) hair manually cut in snippets and extracted at room temperature; (b) pulverised hair extracted at room temperature; (c) hair treated with the optimised method. Average increments of EtG concentration around 69% (from a to c) and 29% (from b to c) were recorded. In light of these results, the authors urge the scientific community to undertake an inter‐laboratory study with the aim of defining more in detail the optimal hair EtG detection method and verifying the corresponding cut‐off level for legal enforcements.
The combination of arbuscular mycorrhizal fungi inoculation (Glomus versiforme) and 28‐homobrassinolide spraying intervals improves growth by enhancing photosynthesis, nutrient absorption, and antioxidant system in cucumber (Cucumis sativus L.) under salinity
Authors: Ahmad Husain , Hayat Sikandar , Ali Muhammad , Liu Tao , Cheng Zhihui
Published: May 2018

Salinity is one of the major obstacles in the agriculture industry causing huge losses in productivity. Several strategies such as plant growth regulators with arbuscular mycorrhizal fungi (AMF) have been used to decrease the negative effects of salt stress. In our experiment, 28‐homobrassinolide (HBL) with spraying intervals was combined with AMF (Glomus versiforme) in cucumber cultivars Jinyou 1# (salt sensitive) and (Changchun mici, in short, CCMC, salt tolerant) under NaCl (100 mmol/L). Studies have documented that the foliar application of HBL and AMF colonization can enhance tolerance to plants under stress conditions. However, the mechanism of the HBL spraying intervals after 15 and 30 days in combination with AMF in cucumber under salt stress is still unknown. Our results revealed that the HBL spraying interval after 15 days in combination with AMF resulted in improved growth, photosynthesis, and decreased sodium toxicity under NaCl. Moreover, the antioxidant enzymes SOD (superoxide dismutase; EC 1.15.1.1) and POD activity (peroxidase; EC 1.11.1.7) showed a gradual increase after every 10 days, while the CAT (catalase; EC 1.11.1.6) increased after 30 days of salt treatments in both cultivars. This research suggests that the enhanced tolerance to salinity was mainly related to elevated levels of antioxidant enzymes and lower uptake of Na+, which lowers the risk of ion toxicity and decreases cell membrane damage.
Mechanistic Insights into the Decarboxylative Electrophilic Trifluoromethylthiolation of β‐Ketocarboxylic Acids
Authors: Guyon Hélène , Chachignon Hélène , Tognetti Vincent , Joubert Laurent , Cahard Dominique
Published: May 2018

A metal‐free protocol for the domino trifluoromethylthiolation/decarboxylation of β‐ketocarboxylic acids is described. The catalytic reactions take place in acetonitrile in the presence of aqueous ammonium hydroxide and N‐trifluoromethylthiosaccharin. The sequence of events and reaction mechanism were established experimentally and using density functional theory calculations. This synthetic method offers a convenient alternative to known routes for the synthesis of α‐trifluoromethylthio‐substituted ketones.
Hybrid Electronic Tongue as a Tool for the Monitoring of Wine Fermentation and Storage Process
Authors: Kutyła‐Olesiuk Anna , Wesoły Małgorzata , Wróblewski Wojciech
Published: May 2018

Hybrid electronic tongue based on potentiometric and voltammetric sensors was applied for the monitoring of wine production process. The sensor array formed by miniaturized ion‐selective electrodes and glassy carbon electrodes provided the analysis of the progress and correctness of wine fermentation and storage process, detection of the presence of disturbing factors and evaluation of the quality of final product. The efficiency of the proposed approach was compared with the monitoring of wine production carried out using standard reference methods. The results indicated that hybrid electronic tongue could be used as simple and reliable analytical tool dedicated to qualitative and quantitative assessment of wine production.
Iso Points in Electrochemistry. Classification and Verification by Experiment and Theory
Authors: Skitał Piotr M. , Sanecki Przemysław T. , Saletnik Dorota
Published: May 2018

The experimental examples of occurrence of isoalpha points (iap) in electroreduction of Cu2+, Tl+, Zn2+ in the presence of 1,3‐dimethyl‐2‐thiourea have been presented. The theoretical ECE and EE model examples of iap and isopotential point (ipp) as well as mixed iap/ipp isopoints are discussed in the context of their similarities and differences. Novel extended interpretation of ipp points in electrochemistry, based on concentration profiles approach, was also introduced.
Tellurium Film Electrodes Deposited on Carbon and Mesoporous Carbon Screen‐printed Substrates for Anodic Stripping Voltammetric Determination of Copper
Authors: Bobrowski Andrzej , Królicka Agnieszka , Śliwa Julia , Zarębski Jerzy , Economou Anastasios , Kalcher Kurt
Published: May 2018

The performance of screen‐printed electrodes modified in situ with tellurium film for the anodic stripping voltammetric (ASV) determination of Cu(II) is reported. It was found that two types of screen‐printed substrates, namely carbon and mesoporous carbon, were optimal for this application. The selected in situ tellurium film modified electrodes were applied for the square wave ASV determination of copper at μg L−1 concentration levels. Well‐defined and reproducible Cu oxidation stripping peaks were produced at a potential more negative than the anodic dissolution of tellurium. The highest sensitivity of Cu determination was achieved in 0.05 M HCl containing 50 μg L−1 Te(IV) after 300 s of accumulation at −0.5 V. Using the optimized procedure, a linear range from 2 to 35 μg L−1 of Cu(II) was obtained with a detection limit of 0.5 μg L−1 Cu(II) (S/N=3) for 300 s of deposition time. Both sensors, carbon TeF‐SPE and mesoporous carbon TeF‐SPE, were successfully applied for the quantification of Cu in a certified reference surface water sample.
Geodiversity decreases shrub mortality and increases ecosystem tolerance to droughts and climate change
Authors: Stavi Ilan , Rachmilevitch Shimon , Hjazin Amgad , Yizhaq Hezi
Published: May 2018

Mass mortality of shrubs, especially the Noaea mucronata species, has been observed in the semi‐arid Negev of Israel since the early twenty‐first century. This has followed a long‐term drought episode, and suggests a hysteresis‐like effect. However, recent studies have revealed that the mortality has been varied across the region. Therefore, we assessed the depth and stoniness of the soil profile, in homogeneous and heterogeneous hillslopes. Then, we studied the volumetric moisture content during two consecutive growing seasons, in the topsoil of shrubby patches and of inter‐shrub spaces in these hillslopes. The study shows that geodiversity – characterized by shallow soil, a high content of stones in the soil, and a high cover of rock fragment on the surface – reduced shrub mortality. This was attributed to the soil moisture content, which was considerably greater in the heterogeneous hillslopes, than that in the homogeneous hillslopes. It is proposed that the shallow soil halted the growth of herbaceous vegetation in the inter‐shrub spaces of the heterogeneous hillslopes. Therefore, under rainstorms, this hillslope configuration results in considerable generation of overland water flow in the inter‐shrub spaces. The water accumulates in the shrubby patches, allowing them to thrive, even during long‐term dry episodes. In hillslopes with a deep soil layer, no stoniness in the soil profile, and no cover of rock fragments, the herbaceous vegetation is well developed, covering a considerable share of the inter‐shrub spaces. This negates runoff formation and source–sink relations, limiting water availability for the shrubs, and resulting in their mass mortality. Despite no direct pastoral value for livestock, the shrubs play an important role in overall ecosystem functioning. This is due to their capacity to transect hydraulic connectivity, and negate ecosystem collapse. We propose a conceptual model for demonstrating the role played by geodiversity in alleviating drought stress in drylands. Copyright © 2018 John Wiley & Sons, Ltd.