bluuebunny/crossref_metadata_2025 huggingface dataset:
Valorization of Waste: Sustainable Organocatalysts from Renewable Resources
Authors: Meninno Sara
Published: October 2019

One of the greatest challenges facing our society is to reconcile our need to develop efficient and sophisticated chemical processes with the limited resources of our planet and its restricted ability to adsorb pollution. Organocatalysis has allowed many issues to be addressed in the development of sophisticated, but less polluting, processes. However, minimizing waste also means an efficient utilization of raw and renewable materials. Waste biomass represents an alternative to conventional petroleum‐based chemical manufacturing and is a highly attractive renewable resource for the production of chemicals and high‐value‐added organocatalysts. Recent achievements in the use of renewable biomass feedstocks for the synthesis of organocatalysts are presented. Their application in synthetic methodologies, including multicomponent reactions, which are performed under solvent‐free conditions or in eco‐friendly reaction media, as well as recycling and reusing the organocatalysts, is illustrated. A few pioneering examples that demonstrate the potential of these promoters in asymmetric synthesis have also been documented. In particular, this review covers examples on the use of hetero‐ and homogeneous organocatalysts derived from 1) waste biopolymers, such as chitosan, alginic acid, and cellulose; ii) renewable platform molecules, such as levoglucosenone, isosorbide, mannose, d‐glucosamine, and lecithin; 3) terpenes and rosin, such as pinane, isosteviol, and abietic acid; and iv) natural proteins (gelatin, bovine tendons, silk fibroin proteins).
A naturalistic investigation of cognitive‐affective dysfunction in anorexia nervosa: The role of inefficiency
Authors: Fürtjes Sophia , Seidel Maria , King Joseph A. , Boehm Ilka , Jaite Charlotte , Roessner Veit , Ehrlich Stefan
Published: October 2019

Objective

Research has shown that rumination and negative affect are elevated in patients with anorexia nervosa (AN), but the underlying origins remain unclear. Drawing from the theoretical framework of the Goal Progress Theory of rumination, we propose that heightened feelings of “inefficiency” (i.e., low self‐efficacy) in AN might play an important role in these dysfunctional cognitive‐affective processes.

Method

Thirty‐two weight‐recovered participants with a history of AN and 32 healthy control participants filled out questionnaires regarding rumination and affect six times a day over a period of 2 weeks via ecological momentary assessment in real‐life.

Results

Analyses via hierarchical as well as conceptual process modeling suggest that while inefficiency is generally associated with more rumination and negative affect, additional amplifying mechanisms between these variables exist specifically in recovered participants with a history of AN.

Discussion

Inefficiency as a core aspect of AN appears to trigger dysfunctional cognitive‐affective processes which may contribute to vulnerability for AN.
Evaluation of the genotoxicity of cell phone radiofrequency radiation in male and female rats and mice following subchronic exposure
Authors: Smith‐Roe Stephanie L. , Wyde Michael E. , Stout Matthew D. , Winters John W. , Hobbs Cheryl A. , Shepard Kim G. , Green Amanda S. , Kissling Grace E. , Shockley Keith R. , Tice Raymond R. , Bucher John R. , Witt Kristine L.
Published: October 2019

The National Toxicology Program tested two common radiofrequency radiation (RFR) modulations emitted by cellular telephones in a 2‐year rodent cancer bioassay that included interim assessments of additional animals for genotoxicity endpoints. Male and female Hsd:Sprague Dawley SD rats and B6C3F1/N mice were exposed from Gestation day 5 or Postnatal day 35, respectively, to code division multiple access (CDMA) or global system for mobile modulations over 18 hr/day, at 10‐min intervals, in reverberation chambers at specific absorption rates of 1.5, 3, or 6 W/kg (rats, 900 MHz) or 2.5, 5, or 10 W/kg (mice, 1,900 MHz). After 19 (rats) or 14 (mice) weeks of exposure, animals were examined for evidence of RFR‐associated genotoxicity using two different measures. Using the alkaline (pH > 13) comet assay, DNA damage was assessed in cells from three brain regions, liver cells, and peripheral blood leukocytes; using the micronucleus assay, chromosomal damage was assessed in immature and mature peripheral blood erythrocytes. Results of the comet assay showed significant increases in DNA damage in the frontal cortex of male mice (both modulations), leukocytes of female mice (CDMA only), and hippocampus of male rats (CDMA only). Increases in DNA damage judged to be equivocal were observed in several other tissues of rats and mice. No significant increases in micronucleated red blood cells were observed in rats or mice. In conclusion, these results suggest that exposure to RFR is associated with an increase in DNA damage. Environ. Mol. Mutagen. 61:276–290, 2020. © 2019 Wiley Periodicals, Inc.
Investigation of the factors influencing methane adsorption on illite
Authors: Xiong Jian , Liu Xiangjun , Liang Lixi , Wei Xiaocheng , Xu Peng
Published: October 2019

The molecular simulation method was used to investigate the adsorption behaviors of methane on illite. The effects of several factors on methane adsorption, free gas amounts, and the proportions of absorbed gas in the illite nanopores, including the pore size, temperature, and water content, are discussed. The results obtained show that methane adsorption in illite nanopores is due mainly to van der Waals adsorption. With an increase in the pressure or of the pore size, the free gas amounts of methane increase, whereas the free gas amounts decrease with increasing temperature or water content. With increasing pressures or decreasing pore sizes, the methane adsorption capacity of the illite pores increases. When the pressure or pore size increases, the proportion of the adsorbed gas in the pores decreases. As the temperature increases, the methane adsorption capacity of the illite pores decreases, and the proportion of adsorbed gas in the illite pores decreases slightly. The adsorbed phase density decreases with increasing pore size and temperature, whereas the adsorbed phase density increases with increasing pressure. The electrostatic forces and hydrogen bonds have a positive effect on water adsorption in the illite nanopores, while the van der Waals forces have the opposite effect, which causes the water molecules in the illite pores to exist in the form of aggregates. The water molecules occupy the areas near the pore walls in a directional manner and occupy the adsorption space and the adsorption sites of methane, resulting in a decrease in the methane adsorption capacity and a slight reduction in the proportion of adsorbed gas.
High‐frequency standard deviation of the capacity factor of renewable energy facilities: Part 1—Solar photovoltaic
Authors: Boretti Alberto
Published: October 2019

It is important to secure for every solar photovoltaic energy installation the highest‐possible average (mean) capacity factor, as well as the lowest‐possible SD, this latter computed with high frequency. High‐frequency data of solar photovoltaic energy facilities are, however, very hard to be found. There are no estimations in the literature of the SD of the capacity factor of solar photovoltaic energy installations sampled with high frequency. Here, we show the data sampled every 5 minutes for the solar photovoltaic energy facilities connected to the Australian National Electricity Market grid during the year 2018. The average capacity factors are about 27%‐28% flat panel, and 31%‐32% tracking flat panel. The SDs have larger values at about 37%‐38%, for coefficients of variation 120%‐130%. As solar photovoltaic energy facilities only produce electricity during the daylight time, that is predictable, the statistic analysis is also applied to the daylight times only. While average daylight‐only capacity factors are about twice the previous values, SDs are slightly less, for coefficients of variations more than halved at 55%‐65%. The analysis highlights the extreme variability of solar energy helping the design of the energy storage needed for making possible an efficient, resilient, renewable energy‐only grid. The collected and interpreted information and the provided analysis are filing a gap in the area of renewable energy and energy harvesting technology based on wind and solar photovoltaics where variability has been so far underevaluated.
Heavy Metal, Arsenic, and Selenium Concentrations in Bird Feathers from a Region in Southern China Impacted by Intensive Mining of Nonferrous Metals
Authors: He Chao , Su Tongping , Liu Shilong , Jiang Aiwu , Goodale Eben , Qiu Guangle
Published: October 2019

Heavy metal pollution is widespread in China, particularly in its mining regions. Mercury (Hg) concentrations in birds from Guizhou Province were recently reported to be above adverse effect levels, even in nonmining areas. We sampled birds to investigate whether Hg might be a threat near lead (Pb), zinc (Zn), and tin (Sn) mines in Guangxi Zhuang Autonomous Region. We measured concentrations of 8 metals/metalloids in feathers of 627 resident birds representing 60 species sampled across 14 sites on 5 rivers. We found that Hg concentrations (mean ± standard deviation, 1.27 ± 2.02 ppm) were lower than in the recent Guizhou study. Mercury had the fewest correlations with other metals/metalloids; the mined metals (Pb, Sn, Zn) had the most such correlations. Levels of cadmium (Cd; 1.12 ± 2.64 ppm), arsenic (As; 4.78 ± 17.11 ppm), and Pb (17.18 ± 24.49 ppm) were closer to thresholds of adverse effects or relatively high compared to other studies. With the exception of a few hot spots for Hg, Cd, and As near mines, metal/metalloid levels were fairly evenly distributed among sites, consistent with the regional occurrence of mineable ore deposits. It appears that Hg is not threatening to all avian species in China, although it may be problematic for some species near Hg mines. In addition to Hg, however, other metals/metalloids may pose wildlife health hazards. Environ Toxicol Chem 2020;39:371–380. © 2019 SETAC
Characterization of volatile and odor‐active compounds of the essential oil from Bidens graveolens Mart. (Asteraceae)
Authors: Silva Ana C. R. , Bizzo Humberto R. , Vieira Roberto F. , Bringel João B. A. , Azevedo Débora A. , Uekane Thais M. , Rezende Claudia M.
Published: October 2019

During a bioprospection study in the Brazilian Cerrado, samples of Bidens graveolens Mart., an endemic species, were investigated. Chemical and olfactive analyses were performed on the essential oil obtained from fresh leaves of B. graveolens collected in November 2013 (BG1) and May 2014 (BG2). A total of 60 compounds were identified in the essential oil extracted from fresh leaves, by hydrodistillation. The main constituents were identified as monoterpene hydrocarbons, ranging from 86.5% to 89.6%. Limonene was the major compound, accounting for 22.8% in BG1 and 47.7% in BG2. Thirty‐three–oxygenated monoterpenes were identified, comprising about 9% in both essential oils (EO). The attributes described by the panelists are in accordance to the sensorial profile. Myrcene, limonene, epoxy‐myrcene, and limonene dioxide were rated by all panelists. Present at a frequency of 83.3%, α‐pinene, β‐pinene, α‐pinene oxide, and carvone were picked out by five panelists. It is noteworthy that most compounds rated with the highest intensity score belonged to the oxygenated monoterpene class, considered the most expressive terpene class used in perfumery. In general, these compounds were described as presenting green, herb, spicy, fresh, and camphoraceus odors.
An extragonadal yolk sac tumor presumed to be of postmeiotic germ cell origin by genetic zygosity analysis via single nucleotide polymorphism array
Authors: Tamura Daisuke , Maeda Daichi , Sato Toshiharu , Sugawara Tae , Shirasawa Hiromitsu , Shimizu Dai , Sato Naoki , Goto Akiteru , Terada Yukihiro
Published: October 2019

An extragonadal yolk sac tumor (YST) is a rare malignant germ cell tumor that usually occurs in childhood. The pathogenesis of extragonadal YST remains largely unknown, especially with regards to its cell of origin. Herein, we report a case of extragonadal YST arising in the uterine round ligament. A 31‐year‐old Japanese woman, para 2, underwent partial resection of a left‐sided, 5‐cm, solid inguinal mass. Intraoperative findings showed enlargement of the uterine round ligament in the inguinal canal. Pathological evaluation diagnosed the mass as YST with a mature teratoma (MT) component. The preoperative α‐fetoprotein level was markedly elevated, at 24 790 ng/mL. Postoperative magnetic resonance imaging revealed a right ovarian MT and a 3‐cm mass remaining in the left lower abdominal wall. The patient underwent total abdominal hysterectomy, bilateral adnexectomy, and left inguinal mass resection. We sampled three frozen tissues (YST, right ovarian MT, and left normal ovary) and performed a single nucleotide polymorphism (SNP) array. Pathological evaluation revealed remnant extragonadal YST in the left inguinal region. The SNP array demonstrated a completely homozygous YST genotype. Copy number variations were gains of 1p, 1q, 2p, 3p, 7p, 8p, 10q, 14q, 18p, 20q, Xp, and Xq and losses of 12q, 20p, and Xq. The right ovarian MT and left normal ovary were partially homozygous and heterozygous, respectively. The evidence suggests that this neoplasm is presumed to be a postmeiotic germ cell origin.
Combined assessment of 3q26 amplification and promoter methylation in patients with high grade cervical lesions show age specific differences
Authors: Beiersdorf Josefine , Scheungraber Cornelia , Wunsch Kristina , Schmitz Martina , Hansel Alfred , Hoyer Heike , Gajda Mieczyslaw , Greinke Christiane , Runnebaum Ingo B. , Dürst Matthias , Backsch Claudia
Published: October 2019

A considerable proportion of high grade cervical intraepithelial lesions (CIN2/3) are known to resolve on their own especially among young women. However, since reliable prognostic markers are still lacking, the diagnosis “CIN3” is still an indication for surgery which may result in overtreatment. It is conceivable that a combination of different, ideally independent molecular markers may provide more reliable results. In the present cross‐sectional study two established triage markers, 3q26 amplification and a methylation signature, were evaluated in an age‐dependent manner. The patient cohort comprised 60 patients with histologically confirmed CIN2/3 in two equally sized age groups (<30 years, ≥30 years). Cervical scrapes were analyzed by interphase fluorescence in situ hybridization for 3q26 amplification and methylation specific PCR (GynTect®) for six different genome regions. Both assays showed a significantly different pattern of test outcome independent of age (P = .001). Moreover, the combination of both assays differed significantly for double positive and double negative cases when comparing the two age groups: In patients <30 years there were clearly less cases with positive methylation signature and amplification of 3q26 as in women ≥30 years (23% vs 63%, Bonferroni adjusted P = .016). Of particular interest is the finding that double negative results were exclusive for the young age group (0% vs 27%, Bonferroni adjusted P = .020). Since regression of CIN2/3 characteristically occurs among young women it is tempting to speculate that a double negative test result could be prognostic for regression of CIN2/3. This will have to be investigated further in a prospective longitudinal intervention study.
Total Synthesis and Biological Evaluation of Heliolactone
Authors: Yoshimura Masahiko , Fonné‐Pfister Raymonde , Screpanti Claudio , Hermann Katrin , Rendine Stefano , Dieckmann Michael , Quinodoz Pierre , De Mesmaeker Alain
Published: October 2019

Strigolactones are phytohormones, which affect diverse aspects of plant growth and development with potential application in modern agriculture. Recently, heliolactone has been isolated as a non‐canonical type of strigolactone from the root exudates of sunflower, and it could be involved in signaling in the rhizosphere as well as in planta. However, its biological activity is yet to be evaluated, due to its relative chemical instability and its low natural abundance. Herein, we describe the gram‐scale synthesis of heliolactone and its derivatives by using Stille cross‐coupling as the key bond‐forming reaction, and we disclose some of their biological activities (soil stability, binding ability to strigolactone receptor, corn germination, sunflower germination, Orobanche cumana germination and leaf senescence) in comparison with other canonical and non‐canonical strigolactones.
Why Do We Need More Active ATRP Catalysts?
Authors: Lorandi Francesca , Matyjaszewski Krzysztof
Published: October 2019

Atom transfer radical polymerization (ATRP) is a staple technique for the preparation of polymers with well‐defined architecture. In ATRP, the catalyst governs the equilibrium between propagating radicals and dormant species, thus affecting the polymerization control for a range of monomers and transferable atoms employed in the process. The design and the use of highly active catalysts could diminish the amount of transition metal complexes, extend ATRP to less active monomers and give access to new chain‐end functionalities. At the same time, very active catalysts can be involved in formation of organometallic species. Herein, the role of the catalyst on the ATRP equilibrium is carefully elucidated, together with recent observations on the impact of the catalyst nature on formation of organometallic species and relevant side reactions. Based on this knowledge, a perspective on the benefits and challenges that derive from the use of highly active ATRP catalysts is presented.
The atherogenic role of immune cells in familial hypercholesterolemia
Authors: Taghizadeh Eskandar , Taheri Forough , Gheibi Hayat Seyed Mohammad , Montecucco Fabrizio , Carbone Federico , Rostami Daryoush , Montazeri Ardalan , Sahebkar Amirhossein
Published: October 2019

Familial hypercholesterolemia (FH) is an autosomal dominant disorder of lipoprotein metabolism that mainly occurs due to mutations in the low‐density lipoprotein receptor gene and is characterized by increased levels of low‐density lipoprotein cholesterol, leading to accelerated atherogenesis and premature coronary heart disease. Both innate and adaptive immune responses, which mainly include monocytes, macrophages, neutrophils, T lymphocytes, and B lymphocytes, have been shown to play a key role for the initiation and progression of atherogenesis in the general population. In FH patients, these immune cells have been suggested to play specific pro‐atherosclerotic activities, from the initial leukocyte recruitment to plaque rupture. In fact, the accumulation of cholesterol crystals and oxLDL in the vessels in FH patients is particularly high, with consequent abnormal mobilization of immune cells and secretion of various pro‐inflammatory and chemokines. In addition, cholesterol accumulation in immune cells is exaggerated with chronic exposure to relevant pro‐atherosclerotic triggers. The topics considered in this review may provide a more specific focus on the immune system alterations in FH and open new insights toward immune cells as potential therapeutic targets in FH.
Vitamin A administration in lizards during tail regeneration determines epithelial mucogenesis and delays muscle and cartilage differentiation
Authors: Alibardi Lorenzo
Published: October 2019

Regenerating epidermis and spinal cord is essential to maintain tail regeneration in lizards. The effects of vitamin A, an inhibitor of epithelial cornification, have been studied in lizards during tail regeneration. The injection of high doses of vitamin A induces regeneration of a thinner tail with gummy consistency and suppression of the formation of a normal cartilaginous axial skeleton. Microscopic analysis reveals that all epithelia increase the secretion of glycoprotein‐mucus. During the analyzed period the epidermis does not form scales and keratinocytes limit or stop the production of bundles of intermediate filament keratins and packets of corneous beta‐proteins (β‐keratins). Differentiation of oberhautchen and β‐layers is much reduced or inhibited while α‐keratinization and the formation of a corneous layer are affected as well. The effects of vitamin A are dramatic also on mesoderm cells since the treatment stimulates an invasion of blood cells likely due to the disruption of the wall of blood vessels, mesenchymal cell death (pycnosis), and diffuse phagocytosis by immune cells. A delay of cartilage differentiation and cartilage degradation due to an increase of lysosomes in these cells or released by white blood cells explains the lack of stiffness of the regenerating tail after vitamin A treatment. Regenerating muscles are variably affected, ranging from a variable necrotic effect with partial degradation of internal organelles and myofilaments to a massive or complete loss of myofibrils that do not organize in sarcomeres. In general hypervitaminosis A appears to delay epithelial but also mesodermal cell differentiation and maintains the regenerating tail in an immature condition.
Access to prevention of mother‐to‐child transmission of HIV along HIV services cascade through integrated active case management in 15 operational districts in Cambodia
Authors: Samreth Sovannarith , Keo Vannak , Tep Romaing , Ke Angheng , Ouk Vichea , Ngauv Bora , Mam Sovatha , Ferradini Laurent , Ly Penh S , Mean Chhi V , Delvaux Therese
Published: October 2019

Introduction

Following the introduction of option B+ in 2013, and with the perspective of eliminating mother‐to‐child transmission of HIV by 2025, Cambodia has implemented an integrated active case management (IACM) approach since 2014 to improve the notification and follow‐up of all HIV‐infected cases including pregnant women, and to ensure access to and use of the full prevention of mother‐to‐child transmission (PMTCT) service package by HIV‐infected pregnant women and their HIV‐exposed infants. This study aimed to analyse PMTCT cascade data in 15 operational districts (ODs) implementing the IACM approach in Cambodia.

Methods

We analysed PMTCT cohort data from 15 ODs implementing IACM approach between 1 January 2014 and 31 December 2016. We measured key indicators along the PMTCT cascade and compared them to available (cross‐sectional) PMTCT indicators during the 2011 to 2013 period.

Results

During the period 2014 to 2016, among 938 identified HIV‐infected pregnant women, 308 (32.8%) were tested HIV positive during their pregnancy, 9 (1.0%) during labour, while the remaining 621 (66.2%) were women on antiretroviral therapy (ART) who became pregnant. During the study period, 867 (92.4%) of the 938 women received ART during pregnancy and labour. Subsequently, 456 (85.6%) of the 533 HEI born and alive during the study period received 6‐week antiretroviral (ARV) prophylaxis, 390 (76.6%) and 396 (77.8%) of the 509 infants aged six weeks or older received cotrimoxazole prophylaxis and HIV‐DNA PCR test respectively. Among the 396 HEI who received HIV‐DNA PCR test, 7 (1.8%) were found HIV positive. The comparison with cross‐sectional PMTCT indicator obtained during the previous 2011 to 2013 period in the same 15 ODs, showed a significant increase in ARV uptake among HIV‐infected pregnant women (from 72.3% to 92.4%), in cotrimoxazole uptake (from 41.6% to 73.2%), and in HIV‐DNA PCR testing coverage among HEI (from 41.2% to 74.3%).

Conclusions

The implementation of option B+ and IACM may have contributed to the improvement of the PMTCT cascade in Cambodia. However, some gaps in accessing PMTCT services along the HIV cascade persist and need to be addressed.
A reassessment of the cranial morphology of Neoepiblema acreensis (Rodentia: Chinchilloidea), a Miocene rodent from South America
Authors: Kerber Leonardo , Ferreira José D. , Negri Francisco R.
Published: October 2019

The rodent Neoepiblema acreensis (Chinchilloidea: Neoepiblemidae) is member of a lineage that reached gigantic dimensions during the Late Miocene of South America—the Neoepiblemidae. In this paper, the cranial anatomy of this rodent is reviewed. Noninvasive imaging is used to reveal internal structures. Our review is based mainly on an almost complete cranium from the Upper Miocene deposits of the western Amazonia of Brazil. The cranium has an elongated rostrum, large frontal sinuses, a deep temporal fossa, well‐developed sagittal, nuchal, medial occipital, and secondary crests, and a tympanic fenestra connected to the external acoustic meatus by a thin ventral cleft. Remarkably, the cranium shows the presence of fossae on the posterior region of the frontal and parietal bones, and a “W‐shaped” fronto‐parietal suture, which are not present in other analyzed chinchilloids. This study contributes to the knowledge of the morphology of this extinct rodent as well as to the phylogenetic relationships and paleobiology of neoepiblemids.
Assessment of uncertainty in multi‐model means of downscaled South Florida precipitation for projected (2019–2099) climate
Authors: Infanti Johnna M. , Kirtman Ben P. , Aumen Nicholas G. , Stamm John , Polsky Colin
Published: October 2019

South Florida resource management, particularly the Everglades restoration effort, is beginning to consider projections of precipitation from multiple climate models for decision‐making. Because precipitation changes can significantly affect the Everglades ecosystem, characterization of precipitation projection uncertainty is important for resource management decisions, and reduction of uncertainty is desired for better decision‐making. Though uncertainty of precipitation projections has been characterized for many regions, uncertainty has not been sufficiently quantified for South Florida. This study builds upon prior results for projected Florida precipitation by considering recent climate model simulations, seasonal and spatial information, and uncertainty quantification and reduction. We identify the multi‐model mean change in South Florida precipitation and characterize the uncertainty of 37 statistically downscaled Coupled Model Intercomparison Project Phase 5 models. For 2019–2045, there is a likely (over 60% of ensemble members) increase in South Florida annual mean precipitation owing to a likely to very likely (near 90% of ensemble members) increase in dry season (November, December, and January) precipitation, while wet season (June, July, and August) shows a more likely than not (over 50% of ensemble members) decrease in precipitation in the southern region and increase in precipitation in the northern region of South Florida. As South Florida agencies are on the verge of including precipitation projections in their upcoming planning horizon, this information will aid South Florida climate data users in decisions influenced by future rainfall.
Development of a near‐real‐time global in situ daily precipitation dataset for 0000–0000 UTC
Authors: Yang Su , Jones Phil D. , Jiang Hui , Zhou Zijiang
Published: October 2019

In this study, we have developed a global in situ daily precipitation dataset based on quasi‐real‐time sub‐daily observations of precipitation totals for the 0000–0000 UTC (Co‐ordinated Universal Time) day everywhere in the world. The sub‐daily precipitation data from meteorological stations are obtained via the World Meteorological Organization's (WMO) Global Telecommunication System (GTS) and China Meteorological Administration Net (CMANet) archived by the National Meteorological Information Centre (NMIC) in China and the Integrated Surface Database (ISD) released by the National Centers for Environmental Information (NCEI) in the USA. We have combined these three sources into a global dataset, referred to as NMIC. Accumulated precipitation totals (depending on the country and the WMO region) are transmitted at a variety of times on the GTS. Of these, about 4,500 stations report daily for the 0000–0000 UTC day. Here, we significantly add to this, by developing two‐way accumulation algorithms to decompose other reported sub‐daily totals to shorter intervals, and then re‐cumulate them where possible to the 0000–0000 UTC day. Using these algorithms, we increase by 51.1% of the number of stations during 2009–2016 to around 6,800 day−1. Additionally, date boundary adjustment (sliding between 1 and 6 hours either side of 0000 UTC) raises the data volume to between 7,800 and 8,700 day−1. We compare our NMIC product with the First Guess Daily (FGD) product from the Global Precipitation Climatology Centre (GPCC) and GHCN‐Daily from NCEI (National Centers for Environmental Information). Root mean square differences between our NMIC and GPCC FGD products over the 2009–2016 period are around 3.4–3.7 mm·day−1 and the average consistency percentage is about 75.1–76.8%. Greater differences between NMIC and GHCN‐daily are found which are probably due to the non‐uniform date boundary in GHCN‐Daily.
Removing the fuzziness in medical device manufacturing R&D
Authors: Tan Cheng Ling , Yee Yann Mey , Mohd Nasurdin Aizzat , Yeo Sook Fern
Published: October 2019

Ensuring regulatory compliance plays a significant part in the cost of research and development (R&D) in any sector where the work is inherently unstructured, or fuzzy. This includes aircraft manufacturing, pharmaceuticals, and the medical device industry, which produces instruments for use in medical procedures. A study of a medical device manufacturer gives insight into the problem of fuzziness in the R&D phase and shows how interconnecting the different functions of the business can contain costs. Doing so entails nurturing strong supplier‐customer relationships, sharing knowledge, and fostering a fulfillment‐oriented organizational culture that values lifelong learning.
Effects on hip stress following sacroiliac joint fixation: A finite element study
Authors: Joukar Amin , Chande Ruchi D. , Carpenter R. Dana , Lindsey Derek P. , Erbulut Deniz U. , Yerby Scott A. , Duhon Bradley , Goel Vijay K.
Published: October 2019

For those patients who suffer from low back pain generated by the sacroiliac (SI) joint, fusion of the SI joint has proven to be an effective means of stabilizing it and reducing pain. Though it has shown promise, SI joint fusion raises clinical questions regarding its effect on neighboring joints such as the hip. As such, the purpose of this study was to determine the effects of SI joint fixation on the hip. A finite element spine‐sacroiliac‐hip (SSIH) model was developed and its functionality was verified against SI joint range of motion (ROM) and hip contact stress, respectively. The intact model was fixed in double leg stance at the distal femora, and loading was applied at the lumbar spine to simulate stance, flexion, extension, right and left lateral bending, and right and left axial rotation. Functionality was confirmed by measuring and comparing SI joint ROM and contact stress and area at the hip with data from the literature. Following verification of the intact SSIH model, both unilateral and bilateral SI joint fixation were modeled; hip contact stress and area were compared to the intact state. Average hip contact stress was ~2 MPa, with most motions resulting in changes less than 5% relative to intact; contact area changed less than 10% for any motion. Clinical significance: these results demonstrated that SI joint fixation with triangular titanium implants imparted little change in stress at the hip, which suggests that the risk of developing adjacent segment disease is likely low. Future clinical studies may be executed to confirm the results of this computational study.
Simultaneous determination of eight bioactive constituents of Zhi‐Zi‐Hou‐Po decoction in rat plasma by ultra high performance liquid chromatography with tandem mass spectrometry and its application to a pharmacokinetic study
Authors: Zhu Heyun , Guan Jiao , Shi Jianyi , Pan Xu , Chang Sheng , Zhang Tianyi , Feng Bo , Gu Jingkai
Published: October 2019

Zhi‐Zi‐Hou‐Po Decoction, consisting of Gardenia jasminoides Ellis, Magnolia officinalis Rehd. et Wils., and Citrus aurantium L, is a classical Traditional Chinese Medicine formula for the treatment of depression. In order to make good and rational use of this formula in the future, a sensitive, selective, and reliable ultra high performance liquid chromatography with tandem mass spectrometry method was developed for simultaneous determination of two iridoid glycosides (geniposide and genipin gentiobioside), two lignans (honokiol and magnolol), four flavonoid glycosides (isonaringin, naringin, hesperidin, and neohesperidin), the major bioactive constituents of Zhi‐Zi‐Hou‐Po Decoction, in rat plasma using paeoniflorin as internal standard. Plasma samples were pretreated by a simple protein precipitation with acetonitrile. Chromatographic separation was performed on a shim‐pack XR‐ODS C18 column (75 × 3.0 mm, 2.2 µm) using gradient elution with mobile phase consisting of 0.1% formic acid aqueous solution and acetonitrile at a flow rate of 0.5 mL/min. Mass spectrometric detection was conducted on a 3200 QTRAP mass spectrometry equipped with electrospray ionization source in negative ionization mode. Quantification was performed using multiple reactions monitoring mode. Calibration curves exhibited good linearity (r > 0.9947) over a wide concentration range for all analytes, and the lower limits of quantification were 10, 5, 1, 5, 1, 5, 1, and 5 ng/mL for geniposide, genipin gentiobioside, honokiol, magnolol, isonaringin, naringin, hesperidin, and neohesperidin, respectively. The intraday and interday precisions at three quality control levels were less than 12.3% and the accuracies ranged from −11.2 to 10.7%. Extraction recovery, matrix effect, and stability were satisfactory in rat plasma. The validated method was successfully applied to a pharmacokinetic study of the eight analytes after oral administration of Zhi‐Zi‐Hou‐Po decoction to rats.
Enrichments of post‐translational modifications in proteomic studies
Authors: Pieroni Luisa , Iavarone Federica , Olianas Alessandra , Greco Viviana , Desiderio Claudia , Martelli Claudia , Manconi Barbara , Sanna Maria Teresa , Messana Irene , Castagnola Massimo , Cabras Tiziana
Published: October 2019

More than 300 different protein post‐translational modifications are currently known, but only a few have been extensively investigated because modified proteoforms are commonly present in sub‐stoichiometry amount. For this reason, improvement of specific enrichment techniques is particularly useful for the proteomic characterization of post‐translationally modified proteins. Enrichment proteomic strategies could help the researcher in the challenging issue to decipher the complex molecular cross‐talk existing between the different factors influencing the cellular pathways. In this review the state of art of the platforms applied for the enrichment of specific and most common post‐translational modifications, such as glycosylation and glycation, phosphorylation, sulfation, redox modifications (i.e. sulfydration and nitrosylation), methylation, acetylation, and ubiquitinylation, are described. Enrichments strategies applied to characterize less studied post‐translational modifications are also briefly discussed.
Liquid chromatography with tandem mass spectrometry method for trace level analysis of migrated secondary alkanesulfonate from poly(tetramethylene terephthalate) into food simulants
Authors: Narayana Ramesh , Kumar Arun , Vanderweele Chris , Rodgers Patrick A. , Vade Nath Rajesh
Published: October 2019

Secondary alkanesulfonate has been widely used as an antistatic additive in polymers for producing anti‐dust food packaging containers. Currently, no reported method exists for accurate quantification of secondary alkanesulfonate in ethanolic and acidic food simulants. A new liquid chromatography with tandem mass spectrometry method was developed to quantify the migrated amount of secondary alkanesulfonate at trace levels in food simulants from a poly(tetramethylene terephthalate) containing secondary alkanesulfonate. The poly(tetramethylene terephthalate) samples loaded with the antistatic additive were exposed to various food simulants. The collected extracts were directly analyzed by liquid chromatography with tandem mass spectrometry in electrospray ionization negative mode. As secondary alkanesulfonate is a mixture containing C14 to C17 chain lengths, it was separated on a Poroshell 120 EC‐C8 column adopting methanol water gradient program. The migration of secondary alkanesulfonate ranged from 58 to 329 ppb; which is well within the allowed permissible regulatory limits and the adopted method was validated by conducting spiking studies and acceptable recoveries were obtained. The developed method was not only sensitive to detect lower levels of the migrated antistatic additive, but it also avoided more cumbersome sample preparation methodologies like sample enrichment and other derivatization approaches.
How much is the accuracy of activation energy affected by ignoring thermal inertia?
Authors: Vyazovkin Sergey
Published: October 2019

This work estimates the magnitude of the effect of thermal inertia on the value of the activation energy determined from heat‐flux differential scanning calorimetry (DSC) data. The estimates are obtained via analysis of the literature data on crystallization of copper and thermal degradation of isotactic polystyrene (iPS). The copper crystallization data have been obtained for very large masses (200 mg) and fast heating rates up to 80 K min−1. The iPS degradation data have been collected on small masses (3 mg) and at the heating rates up to 20 K min−1. For crystallization of copper, the Kissinger activation energy obtained from the DSC data corrected for thermal inertia is 34% larger than the value estimated from uncorrected data. This difference drops to 8% and becomes statistically insignificant when the fastest heating rate used is decreased to 10 K min−1. For iPS degradation, the difference in the isoconversional activation energies estimated, respectively, from corrected and uncorrected DSC data is less than 3% and is not statistically significant. Overall, the effect of thermal inertia on the activation energy appears negligible provided that DSC measurements are conducted on smaller samples and at slower heating rates, that is, as advised by the International Confederation for Thermal Analysis and Calorimetry (ICTAC) recommendations. It is suggested that the difference in the activation energies should generally be within the typical 5‐10% uncertainty as long as the product of the time constant and the maximum heating rate does not exceed 2‐3 K.
Computed tomography classification of endoscopic retrograde cholangiopancreatography‐related perforation
Authors: Wu Jhong‐Han , Tsai Hong‐Ming , Chen Chiung‐Yu , Wang Yao‐Sheng
Published: October 2019

Endoscopic retrograde cholangiopancreatography (ERCP)‐related perforation leads to high morbidity and mortality. The Stapfer classification divides patients with different perforation locations and suggests management accordingly. The classification may be unknown if perforation is not detected during endoscopy. We classified patients with ERCP‐related perforation (ERP) through computed tomography (CT) and observed the clinical outcomes with varyingly invasive management. Fifty‐two cases of ERP between July 2009 and December 2017 were retrospectively reviewed. Of them, 41 who underwent CT for ERCP were included. According to their CT findings, we divided patients into air‐alone (n = 16), air‐fluid (n = 18), and fluid‐alone (n = 7) groups. Perforation severity was graded using the Clavien‐Dindo classification for surgical complications. Demographic data and clinical outcomes among different groups were analyzed. Fifteen patients (37%) had an unknown Stapfer classification. More than half of the patients in the air‐fluid group had a Clavien‐Dindo complication grade of >3. Four patients underwent surgical repair; all of them were from the air‐fluid group. All patients in the air‐ and fluid‐alone groups underwent medical treatment without need for subsequent salvage surgery. The air‐fluid group had the longest mean hospital stay (25.1 ± 21.9 days) and the exclusive two mortality cases in this study. Patients with ERCP can be divided into groups with different outcomes according to the presence of air or fluid on CT images. Because patients with both air and fluid have the worst clinical outcome, they may require more aggressive treatment than patients with either air or fluid alone.
Early Switch From Tacrolimus to Everolimus After Liver Transplantation: Outcomes at 2 Years
Authors: Saliba Faouzi , Duvoux Christophe , Dharancy Sébastien , Dumortier Jérôme , Calmus Yvon , Gugenheim Jean , Kamar Nassim , Salamé Ephrem , Neau‐Cransac Martine , Vanlemmens Claire , Durand François , Pageaux Georges , Leroy Vincent , Hardwigsen Jean , Gharbi Hakam , Masson Cécile , Tindel Malka , Conti Filomena
Published: October 2019

The observational CERTITUDE study follows liver transplant patients who completed the SIMCER trial. SIMCER randomized patients at month 1 after transplant to everolimus (EVR) with stepwise tacrolimus (TAC) withdrawal or to standard TAC, both with basiliximab induction and mycophenolic acid ± steroids. After completing SIMCER at 6 months after transplant, 65 EVR‐treated patients and 78 TAC‐treated patients entered CERTITUDE. At month 24 after transplant, 34/65 (52.3%) EVR‐treated patients remained calcineurin inhibitor (CNI) free. Mean estimated glomerular filtration rate (eGFR) was significantly higher with EVR versus TAC during months 3‐12. At month 24, eGFR values were 83.6 versus 75.3 mL/minute/1.73 m2, respectively (P = 0.90) and adjusted mean change in eGFR from randomization was −8.0 versus −13.5 mL/minute/1.73 m2 (P = 0.15). At month 24, 45.9%, 31.1%, and 23.0% of EVR‐treated patients had chronic kidney disease stages 1, 2, and 3, respectively, versus 25.7%, 45.7%, and 28.6% of TAC‐treated patients (P = 0.05). Treated biopsy‐proven acute rejection affected 4 EVR‐treated patients and 2 TAC patients during months 6‐24. Adverse events led to study discontinuation in 15.4% and 7.7% of EVR‐treated and TAC‐treated patients, respectively. Grade 3 or 4 hematological events were rare in both groups. A CNI‐free EVR‐based maintenance regimen appears feasible in approximately half of liver transplant patients. It preserves renal function effectively with good efficacy without compromising safety or hematological tolerance.
Synthesis and Aggregation of Polymer‐Amyloid β Conjugates
Authors: Evgrafova Zhanna , Rothemund Sven , Voigt Bruno , Hause Gerd , Balbach Jochen , Binder Wolfgang H.
Published: October 2019

Modulating the assembly of medically relevant peptides and proteins via macromolecular engineering is an important step in modifying their overall pathological effects. The synthesis of polymer–peptide conjugates composed of the amyloidogenic Alzheimer peptide, Aβ1‐40, and poly(oligo(ethylene glycol)m acrylates) (m = 2,3) with different molecular weights (Mn = 1400–6600 g mol−1) is presented here. The challenging conjugation of a synthetic polymer to an in situ aggregating protein is established via two different coupling strategies, only successful for polymers with molecular weights not exceeding 6600 g mol−1, relying on resin‐based synthesis or solution‐based coupling chemistries. The conjugates are characterized by high‐performance liquid chromatography and matrix‐assisted laser desorption ionization time‐of‐flight mass spectrometry. The aggregation of these polymer‐Aβ1‐40 conjugates, as monitored via thioflavine‐T (ThT)‐fluorescence spectroscopy, is accelerated mainly upon attaching the polymers. However, the appearance of the observed fibrils is different from those composed of native Aβ1‐40, specifically with respect to length and morphology of the obtained aggregates. Instead of long, unbranched fibrils characteristic for Aβ1‐40, bundles of short aggregates are observed for the conjugates. Finally, the ThT kinetics and morphologies of Aβ1‐40 fibrils formed in the presence of the conjugates give some mechanistic insights.
Synthesis of Metallopolymers via Atom Transfer Radical Polymerization from a [2Fe‐2S] Metalloinitiator: Molecular Weight Effects on Electrocatalytic Hydrogen Production
Authors: Karayilan Metin , McCleary‐Petersen Keelee Cathleen , Hamilton Meghan O'Brien , Fu Liye , Matyjaszewski Krzysztof , Glass Richard S. , Lichtenberger Dennis L. , Pyun Jeffrey
Published: October 2019

Small molecule biomimetics inspired by the active site of the [FeFe]‐hydrogenase enzymes have shown promising electrocatalytic activity for hydrogen (H2) generation. However, most of the active‐site mimics based on [2Fe‐2S] clusters are not water‐soluble which limits the use of these electrocatalysts to organic media. Polymer‐supported [2Fe‐2S] systems, in particular, single‐site metallopolymer catalysts, have shown drastic improvements for electrocatalytic H2 generation in aqueous milieu. [2Fe‐2S] complexes functionalized within well‐defined macromolecular supports via covalent bonding have demonstrated water solubility, enhanced site‐isolation, and improved chemical stability during catalysis. In this report, the synthesis of a new propanedithiolate (pdt)‐[2Fe‐2S] complex bearing a single α‐bromoester moiety for use in atom transfer radical polymerization (ATRP) is demonstrated as a novel metalloinitiator to prepare water‐soluble poly(2‐dimethylaminoethyl methacrylate) grafted (PDMAEMA‐g‐[2Fe‐2S]) metallopolymers. Using this approach, metallopolymers with controllable molecular weights (Mn = 5–40 kg mol−1) and low dispersity (Đ, Mw/Mn = 1.09–1.36) are prepared, which allows for the first time observation of the effect of the metallopolymers' chain length on the electrocatalytic activity. The ability to control the composition and molecular weight of these metallopolymers enables macromolecular engineering via ATRP of these materials to determine optimal structural features of metallopolymer catalysts for H2 production.
Hydrogel Adhesion by Wrinkling Films
Authors: Kato Masatoshi , Asoh Taka‐Aki , Uyama Hiroshi
Published: October 2019

A novel adhesion control method for hydrogels utilizing swelling‐induced wrinkling gel films is developed. Structures such as flat, crease, and wrinkle at the interface of adhered gels are controlled by swelling ratio of gel films. The role of microstructures at the gel–gel interface is investigated by adhesive strength measurement. Aligned wrinkles are fabricated with anisotropic swelling films. The adhesive strength of hydrogels with wrinkles parallel to tensile direction is larger than that with perpendicular wrinkles. Adhered gels detach without damage to their surfaces when the wrinkle structures are disrupted by peeling of the wrinkled film. Moreover, thermoresponsive film is used to control wrinkle structures at the adhered interface by temperature. The adhered interface is stable in cold water because of the existence of wrinkles; however, they detach in hot water due to wrinkle deformation. By using wrinkle structure at adhesive interfaces, both strong adhesion and easy detachment of hydrogels are achieved.