bluuebunny/crossref_metadata_2025 huggingface dataset:
A multifunctional chemical cue drives opposing demographic processes and structures ecological communities
Authors: Zimmer Richard K. , Ferrier Graham A. , Kim Steven J. , Kaddis Catherine S. , Zimmer Cheryl Ann , Loo Joseph A.
Published: May 2016

Foundation species provide critical resources to ecological community members and are key determinants of biodiversity. The barnacle Balanus glandula is one such species and dominates space among the higher reaches of wave‐swept shores (Northeastern Pacific Ocean). This animal produces a cuticular glycoprotein (named “MULTIFUNCin”) of 199.6 kDa, and following secretion, a 390 kDa homodimer in native form. From field and lab experiments, we found that MULTIFUNCin significantly induces habitat selection by conspecific larvae, while simultaneously acting as a potent feeding stimulant to a major barnacle predator (whelk, Acanthinucella spirata). Promoting immigration via settlement on the one hand, and death via predation on the other, MULTIFUNCin drives opposing demographic processes toward structuring predator and prey populations. As shown here, a single compound is not restricted to a lone species interaction or sole ecological function. Complex biotic interactions therefore can be shaped by simple chemosensory systems and depend on the multifunctional properties of select bioactive proteins.
Controls on carbon storage and weathering in volcanic soils across a high‐elevation climate gradient on Mauna Kea, Hawaii
Authors: Kramer Marc G. , Chadwick Oliver A.
Published: May 2016

Volcanic ash soils retain the largest and most persistent soil carbon pools of any ecosystem. However, the mechanisms governing soil carbon accumulation and weathering during initial phases of ecosystem development are not well understood. We examined soil organic matter dynamics and soil development across a high‐altitude (3,560–3,030 m) 20‐kyr climate gradient on Mauna Kea in Hawaii. Four elevation sites were selected (~250–500 mm rainfall), which range from sparsely vegetated to sites that contain a mix of shrubs and grasses. At each site, two or three pits were dug and major diagnostic horizons down to bedrock (intact lava) were sampled. Soils were analyzed for particle size, organic C and N, soil pH, exchangeable cations, base saturation, NaF pH, phosphorous sorption, and major elements. Mass loss and pedogenic metal accumulation (hydroxlamine Fe, Al, and Si extractions) were used to measure extent of weathering, leaching, changes in soil mineralogy and carbon accumulation. Reactive‐phase (SRO) minerals show a general trend of increasing abundance with increasing rainfall. However carbon accumulation patterns across the climate gradient are largely decoupled from these trends. The results suggest that after 20 kyr, pedogenic processes have altered the nature and composition of the volcanic ash such that it is capable of retaining soil C even where organic acid influences from plant material and leaching from rainfall are severely limited. Carbon storage comparisons with lower‐elevation soils on Mauna Kea and other moist mesic (2,500 mm rainfall) sites on Hawaii suggest that these soils have reached only between 1% and 15% of their capacity to retain carbon. Our results suggest that, after 20 kyr in low rainfall and a cold climate, weathering was decoupled from soil carbon accumulation patterns and the associated influence of vegetation on soil development. Overall, we conclude that the rate of carbon supply to the subsoil (driven by coupling of rainfall above ground plant production) is a governing factor of forms and amount of soil organic matter accumulation, while soil mineralogy remained relatively uniform.
Foliar damage beyond species distributions is partly explained by distance dependent interactions with natural enemies
Authors: Katz Daniel S. W. , Ibáñez Inés
Published: May 2016

Plant distributions are expected to shift in response to climate change, and range expansion dynamics will be shaped by the performance of individuals at the colonizing front. These plants will encounter new biotic communities beyond their range edges, and the net outcome of these encounters could profoundly affect colonization success. However, little is known about how biotic interactions vary across range edges and this has hindered efforts to predict changes in species distributions in response to climate change. In contrast, a rich literature documents how biotic interactions within species ranges vary according to distance to and density of conspecific individuals. Here, we test whether this framework can be extended to explain how biotic interactions differ beyond range edges, where conspecific adults are basically absent. To do so, we planted seven species of trees along a 450‐km latitudinal gradient that crossed the current distributional range of five of these species and monitored foliar disease and invertebrate herbivory over 5 yr. Foliar disease and herbivory were analyzed as a function of distance to and density of conspecific and congeneric trees at several spatial scales. We found that within species ranges foliar disease was lower for seedlings that were farther from conspecific adults for Acer rubrum, Carya glabra, Quercus alba, and Robinia pseudoacacia. Beyond range edges, there was even less foliar disease for C. glabra, Q. alba, and R. pseudoacacia (A. rubrum was not planted outside its range). Liriodendron tulipifera did not experience reduced disease within or beyond its range. In contrast, Quercus velutina displayed significant but idiosyncratic patterns in disease at varying distances from conspecifics. Patterns of distance dependent herbivory across spatial scales was generally weak and in some cases negative (i.e., seedlings farther from conspecific adults had more herbivory). Overall, we conclude that differences in biotic interactions across range edges can be thought of as a spatial extension to the concept of distance dependent biotic interactions. This framework also provides the basis for general predictions of how distance dependent biotic interactions will change across range edges in other systems.
Analysis of low‐density lipoprotein‐associated proteins using the method of digitized native protein mapping
Authors: Jin Ya , Chen Jin , Wang Ahui , Zhang Jun , Chen Shumin , Manabe Takashi , Tan Wen
Published: May 2016

The method of digitized native protein mapping, combining nondenaturing micro 2DE, grid gel‐cutting, and quantitative LC‐MS/MS (in data‐independent acquisition mode, or MSE), was improved by using a new MS/MS mode, ion mobility separation enhanced‐MSE (HDMSE), and applied to analyze the area of human plasma low‐density lipoprotein (LDL). An 18 mm × 4.8 mm rectangular area which included LDL on a nondenaturing micro 2D gel of human plasma was grid‐cut into 72 square gel pieces and subjected to quantitative LC‐MS/MS. Compared with MSE, HDMSE showed significantly higher performance, by assigning 50% more proteins and detecting each protein in more squares. A total of 253 proteins were assigned with LC‐HDMSE and the quantity distribution of each was reconstructed as a native protein map. The maps showed that Apo B‐100 was the most abundant protein in the grid‐cut area, concentrated at pI ca. 5.4–6.1 and apparent mass ca. 1000 kDa, which corresponded to four gel pieces, squares 39–42. An Excel macro was prepared to search protein maps which showed protein quantity peaks localized within this concentrated region of Apo B‐100. Twenty‐two proteins out of the 252 matched this criterion, in which 19 proteins have been reported to be associated with LDL. This method only requires several microliters of a plasma sample and the principle of the protein separation is totally different from the commonly used ultracentrifugation. The results obtained by this method would provide new insights on the structure and function of LDL.
Synthesis of Novel Phthalazino[1,2‐b]quinazolinedione Derivatives: Efficient and Practical Reaction of 2‐Amino‐N′‐Arylbenzohydrazides and 2‐Formylbenzoic Acids
Authors: Arasteh‐Fard Zahra , Dilmaghani Karim Akbari , Saeedi Mina , Mahdavi Mohammad , Shafiee Abbas
Published: May 2016

This work reported the synthesis of novel phthalazino[1,2‐b]quinazolinedione derivatives through the reaction of 2‐amino‐N′‐arylbenzohydrazides and 2‐formylbenzoic acids in the presence of TsOH in EtOH under reflux conditions.
Prospective cohort study of general and central obesity, weight change trajectory and risk of major cancers among Chinese women
Authors: Liu Ying , Warren Andersen Shaneda , Wen Wanqing , Gao Yu‐Tang , Lan Qing , Rothman Nathaniel , Ji Bu‐Tian , Yang Gong , Xiang Yong‐Bing , Shu Xiao‐Ou , Zheng Wei
Published: May 2016

General obesity, typically measured using body mass index (BMI), has been associated with an increased risk of several cancers. However, few prospective studies have been conducted in Asian populations. Although central obesity, often measured using waist–hip ratio (WHR), is more predictive for type 2 diabetes and cardiovascular diseases (CVD) risk than BMI, knowledge of its association with cancer incidence is limited. In a cohort of 68,253 eligible Chinese women, we prospectively investigated the association of BMI, WHR and weight change during adulthood with risk of overall cancer and major site‐specific cancers using multivariate Cox proportional hazard models. Compared to the BMI group of 18.5–22.9 kg/m2, obese (BMI ≥ 30 kg/m2) women were at an increased risk of developing overall cancer (hazard ratio = 1.36, 95% confidence interval = 1.21–1.52), postmenopausal breast cancer (HR: 2.43, 95% CI: 1.73–3.40), endometrial cancer (HR: 5.34, 95% CI: 3.48–8.18), liver cancer (HR: 1.93, 95% CI: 1.14–3.27) and epithelial ovarian cancer (HR: 2.44, 95% CI: 1.37–4.35). Weight gain during adulthood (per 5 kg gain) was associated with increased risk of all cancers combined (HR: 1.05, 95% CI: 1.03–1.08), postmenopausal breast cancer (HR: 1.17, 95% CI: 1.10–1.24) and endometrial cancer (HR: 1.37, 95% CI: 1.27–1.48). On the other hand, WHR was not associated with cancer risk after adjustment for baseline BMI. These findings suggest that obesity may be associated with cancer risk through different mechanisms from those for type 2 diabetes and CVD and support measures of maintaining health body weight to reduce cancer risk in Chinese women.
Physiological influence of silica on germinating pollen as shown by Raman spectroscopy
Authors: Joester Maike , Seifert Stephan , Emmerling Franziska , Kneipp Janina
Published: May 2016

The process of silicification in plants and the biochemical effects of silica in plant tissues are largely unknown. To study the molecular changes occurring in growing cells that are exposed to higher than normal concentration of silicic acid, Raman spectra of germinating pollen grains of three species (Pinus nigra, Picea omorika, and Camellia japonica) were analyzed in a multivariate classification approach that takes into account the variation of biochemical composition due to species, plant tissue structure, and germination condition. The results of principal component analyses of the Raman spectra indicate differences in the utilization of stored lipids, a changed mobilization of storage carbohydrates in the pollen grain bodies, and altered composition and/or structure of cellulose of the developing pollen tube cell walls. These biochemical changes vary in the different species.

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CX3CR1 polymorphisms associated with an increased risk of developmental dysplasia of the hip in human
Authors: Li Lianyong , Wang Xi , Zhao Qun , Wang Enbo , Wang Lili , Cheng Jinshan , Zhang Lijun , Wang Binbin
Published: May 2016

Developmental dysplasia of the hip, also termed congenital hip dislocation, is one of the major causes of children disability and early onset osteoarthritis. Previous study has identified a variant of CX3CR1 underlying this disorder in a large family. However, genetic evidence from population was still lacking. Here, we performed a case‐control association study by genotyping two SNPs of CX3CR1, rs3732378, and rs3732379, in 689 unrelated hip dislocation patients and 689 normal controls. Genotyping results showed significant difference in genotype distributions of both two polymorphisms (p = 0.003 for rs3732378 and p = 0.017 for rs3732379). The minor allele frequency of rs3732378 was higher in cases (4.79%) than in controls (2.47%), predisposing carriers to hip dislocation with a 2.25‐fold risk (OR = 2.25, 95%CI 1.42–3.56) after adjustment for gender. Another SNP, rs3732379, was also significantly associated with an increased risk of hip dislocation (adjusted OR = 1.84, 95%CI 1.19–2.84). Through the population study, we demonstrated that CX3CR1 was candidate for the pathogenesis of the disorder, and identified rs3732378 and rs3732379 as susceptibility loci instead of disease‐causing mutations. © 2016 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res 35:377–380, 2017.
Image analysis‐based modelling for flower number estimation in grapevine
Authors: Millan Borja , Aquino Arturo , Diago Maria P , Tardaguila Javier
Published: May 2016

BACKGROUND

Grapevine flower number per inflorescence provides valuable information that can be used for assessing yield. Considerable research has been conducted at developing a technological tool, based on image analysis and predictive modelling. However, the behaviour of variety‐independent predictive models and yield prediction capabilities on a wide set of varieties has never been evaluated.

RESULTS

Inflorescence images from 11 grapevine Vitis vinifera L. varieties were acquired under field conditions. The flower number per inflorescence and the flower number visible in the images were calculated manually, and automatically using an image analysis algorithm. These datasets were used to calibrate and evaluate the behaviour of two linear (single‐variable and multivariable) and a nonlinear variety‐independent model. As a result, the integrated tool composed of the image analysis algorithm and the nonlinear approach showed the highest performance and robustness (RPD = 8.32, RMSE = 37.1). The yield estimation capabilities of the flower number in conjunction with fruit set rate (R2 = 0.79) and average berry weight (R2 = 0.91) were also tested.

CONCLUSION

This study proves the accuracy of flower number per inflorescence estimation using an image analysis algorithm and a nonlinear model that is generally applicable to different grapevine varieties. This provides a fast, non‐invasive and reliable tool for estimation of yield at harvest. © 2016 Society of Chemical Industry
Complete cytoreductive surgery and hyperthermic intraperitoneal chemotherapy for colorectal peritoneal metastasis in Norway: Prognostic factors and oncologic outcome in a national patient cohort
Authors: Frøysnes Ida S. , Larsen Stein G. , Spasojevic Milan , Dueland Svein , Flatmark Kjersti
Published: May 2016

Background and Objectives

Cytoreductive surgery (CRS) and hyperthermic intraperitoneal chemotherapy (HIPEC) can offer long‐term survival to patients with resectable peritoneal metastasis (PM) from colorectal cancer (CRC), a condition with otherwise dismal prognosis. This study describes short‐ and long‐term outcome in a national patient cohort and aims to identify prognostic factors.

Methods

All patients treated with CRS‐HIPEC for non‐appendiceal PM‐CRC in Norway 2004–2013 were included (n = 119), and outcome and potential prognostic factors were examined using survival‐ and ROC‐curve analysis.

Results

Five‐year overall survival (OS) and disease‐free survival (DFS) were 36% and 14%, respectively, with 45 months median follow‐up. The only factor associated with OS in multivariable analysis was peritoneal cancer index (PCI), with HR 1.05 (1.01–1.09) for every increase in PCI‐score (P = 0.015). Peritoneal relapse was associated with shorter OS than distant metastasis (P = 0.002). ROC‐curves identified PCI > 12 as a marker with 100% specificity for prediction of disease relapse. Severe postoperative complications (Clavien–Dindo ≥ 3) occurred in 15% of patients and there was no 100‐day mortality.

Conclusions

Long‐term outcome was in line with published results, morbidity was acceptable and there was no 100‐day mortality. The results reemphasize CRS‐HIPEC as an important treatment option in PM‐CRC, with particularly good results in patients with PCI < 12. J. Surg. Oncol. 2016;114:222–227. © 2016 Wiley Periodicals, Inc.
Systematic review of surgery for persistent pediatric tracheocutaneous fistula
Authors: Lewis Sean , Arjomandi Hamid , Rosenfeld Richard
Published: May 2016

Objectives

To compare the treatment outcomes and adverse event rates for primary closure compared to simple excision with healing by secondary intention for persistent tracheocutaneous fistula (TCF) in children.

Study Design

Systematic review.

Methods

Systematic review using Preferred Reporting Items for Systematic Reviews and Meta‐Analyses reporting standards. MEDLINE, Embase, Cochrane Library, and manual search were used to identify articles. Inclusion criteria were case series or comparative studies of surgery for persistent TCF in children under age 18 years. Exclusion criteria were age 18 years or older, duplicate patient series, case series with less than two patients, or case reports. Data were pooled using random effects meta‐analysis to assess outcomes, adverse events, and comparative effectiveness.

Results

We identified 14 articles with 413 patients treated with excision with primary closure and 233 patients treated with excision with closure by secondary intention. Pooled success rates were 95.7% with primary closure (95% confidence interval [CI]: 93.1% to 97.4%) and 92.7% with secondary intention (95% CI: 88.4% to 95.4%). Subcutaneous emphysema or urgent airway problems were uncommon, occurring in 3.8% and 3.6% of patients, respectively. Five studies had data suitable for comparative meta‐analysis, which showed no differences by closure technique for treatment success (P = .480), overall complications (P = .551), need for revision surgery (P = .624), or the incidence of subcutaneous emphysema or pneumothorax (P = .512), urgent airway problems (P = .126), wound infection (P = 1.00), or wound dehiscence or fistula (P = .818).

Conclusions

There are no differences in the rates of success or complications with surgical closure of TCF in children, whether performed by primary closure or by secondary intention. Both techniques have high success rates with a low incidence of serious complications. Laryngoscope, 127:241–246, 2017
Effects of pectin supplementation on the fermentation patterns of different structural carbohydrates in rats
Authors: Tian Lingmin , Scholte Jan , Borewicz Klaudyna , van den Bogert Bartholomeus , Smidt Hauke , Scheurink Anton J.W. , Gruppen Harry , Schols Henk A.
Published: May 2016

Scope

We aimed to investigate and compare the effects of four types of pectins on dietary fiber (DF) fermentation, microbiota composition, and short chain fatty acid (SCFA) production throughout the large intestine in rats.

Methods and results

Male Wistar rats were given diets supplemented with or without 3% structurally different pectins for 7 weeks. Different fermentation patterns of pectins and different location of fermentation of pectin and diet arabinoxylans (AXs) in the large intestine were observed. During cecal fermentation, sugar beet pectin significantly stimulated Lactobacillus (p < 0.01) and Lachnospiraceae (p < 0.05). The stimulating effects of sugar beet pectin on these two groups of microbes are stronger than both other pectins. In the cecum, low‐methyl esterified citrus pectin and complex soy pectin increased (p < 0.05) the production of total SCFAs, propionate and butyrate, whereas high‐methyl esterified pectin and sugar beet pectin did not. The fermentation patterns of cereal AXs in the cecum were significantly different upon supplementation of different pectins. These differences, however, became smaller in the colon due to an enhanced fermentation of the remaining DFs.

Conclusion

Dietary supplementation of pectin is a potential strategy to modulate the location of fermentation of DFs, and consequently microbiota composition and SCFA production for health‐promoting effects.
Asymptomatic urinary retention in elderly women upon admission to the Internal Medicine department: A prospective study
Authors: Justo Dan , Schwartz Natalia , Dvorkin Eliyahu , Gringauz Irina , Groutz Asnat
Published: May 2016

Aim

To assess the incidence and associated risk factors of asymptomatic urinary retention in elderly women upon admission to the Internal Medicine department.

Methods

Two hundred and two consecutive elderly women (mean age 84.4 ± 5.7 years) who were admitted to four Internal Medicine departments at a tertiary medical center were prospectively enrolled. All patients underwent post‐void residual urine (PVR) measurements on the morning following the admission day. The measurements were undertaken by using a portable ultrasound bladder scan. Asymptomatic urinary retention was defined as PVR ≥ 200 ml without lower urinary tract symptoms, or abdominal pain, in two consecutive measurements.

Results

Asymptomatic urinary retention was diagnosed in 29 (14.4%) women (mean PVR: 353.1 ± 155.2 ml; range: 200–712 ml). The mean age, prevalence of chronic diseases, and the use of opioid and antimuscarinic drugs were similar in women with versus without asymptomatic urinary retention. A binary logistic regression analysis showed that asymptomatic urinary retention was significantly and independently associated with low mobility, measured by the functional independence measure (FIM) scale (odds ratio = 0.7, 95% confidence interval 0.6–0.9, P = 0.026), and hypothyroidism (odds ratio = 2.4, 95% confidence interval 1.0–5.8, P = 0.049). Among 174 (86.1%) patients in whom thyroid‐stimulating hormone (TSH) serum levels were measured, a statistically significant correlation was demonstrated between TSH values and PVR measurements.

Conclusions

Asymptomatic urinary retention in elderly women upon admission to the Internal Medicine department is not infrequent and is independently associated with hypothyroidism and low mobility. PVR measurements should, therefore, be considered in all women with a low level of mobility and/or hypothyroidism upon admission to the Internal Medicine department. Neurourol. Urodynam. 36:794–797, 2017. © 2016 Wiley Periodicals, Inc.
Prescriber and pharmacy variation in patient adherence to five medication classes measured using implementation during persistent episodes
Authors: Genberg Becky L. , Rogers William H. , Lee Yoojin , Qato Danya M. , Dore David D. , Hutchins David S. , Brennan Troyen , Matlin Olga S. , Wilson Ira B.
Published: May 2016

Purpose

The objective of this study was to determine the fraction of variance in patient‐level medication adherence accounted for by prescribers and pharmacies.

Methods

We used prescription drug claims paid between January 2010 and July 2011 to a national pharmacy benefits manager to define implementation during persistent episodes. Patients in Massachusetts or Rhode Island covered by Blue Cross Blue Shield of Rhode Island and their prescribers were included. Five drug classes were analyzed: angiotensin converting enzyme (ACE) inhibitors, antihyperglycemics (ANHGs), drugs for prostatic hyperplasia (PH), statins, and levothyroxine (THYR). We performed mixed models with random intercepts (drug, patient, prescriber, and pharmacy) and examined the fraction of variance explained at each level using intraclass correlations.

Results

Overall implementation ranged from 87 to 91%. The fraction of the explained variance in implementation to ACEs, ANHG, PH, statins, and THYR accounted for by prescribers was 16.4%, 12.6%, 14.6%, 15.6%, and 15% respectively; and for pharmacies 20.4%, 20%, 15.2%, 10.6%, and 9.4%, respectively.

Conclusions

Prescriber and pharmacy effects accounted for a substantial amount of the explained variance in implementation across all five drug classes. Adherence interventions for chronic conditions that target prescribers and pharmacies, in addition to patients, could be effective and efficient. Copyright © 2016 John Wiley & Sons, Ltd.
High‐grade sarcoma diagnosis and prognosis: Biomarker discovery by mass spectrometry imaging
Authors: Lou Sha , Balluff Benjamin , de Graaff Marieke A. , Cleven Arjen H.G. , Briaire ‐ de Bruijn Inge , Bovée Judith V.M.G. , McDonnell Liam A.
Published: May 2016

The combination of high heterogeneity, both intratumoral and intertumoral, with their rarity has made diagnosis, prognosis of high‐grade sarcomas difficult. There is an urgent need for more objective molecular biomarkers, to differentiate between the many different subtypes, and to also provide new treatment targets. Mass spectrometry imaging (MSI) has amply demonstrated its ability to identify potential new markers for patient diagnosis, survival, metastasis and response to therapy in cancer research. In this study, we investigated the ability of MALDI‐MSI of proteins to distinguish between high‐grade osteosarcoma (OS), leiomyosarcoma (LMS), myxofibrosarcoma (MFS) and undifferentiated pleomorphic sarcoma (UPS) (Ntotal = 53). We also investigated if there are individual proteins or protein signatures that are statistically associated with patient survival. Twenty diagnostic protein signals were found characteristic for specific tumors (p ≤ 0.05), amongst them acyl‐CoA‐binding protein (m/z 11 162), macrophage migration inhibitory factor (m/z 12 350), thioredoxin (m/z 11 608) and galectin‐1 (m/z 14 633) were assigned. Another nine protein signals were found to be associated with overall survival (p ≤ 0.05), including proteasome activator complex subunit 1 (m/z 9753), indicative for non‐OS patients with poor survival; and two histone H4 variants (m/z 11 314 and 11 355), indicative of poor survival for LMS patients.
Cycloaddition of CS2 to N‐benzylaziridine to synthesize N‐benzylthiazolidine‐2‐thione: a novel reaction route proposed by DFT Study
Authors: Singh Amritpal , Goel Neetu
Published: May 2016

N‐Benzylthiazolidine‐2‐thione is the key intermediate for the synthesis of pharmaceutically important compounds. A novel route for the synthesis of N‐benzylthiazolidine‐2‐thione through cycloaddition of CS2 with N‐benzylaziridine in the presence of 1,3‐di‐tert‐butylimidazolium‐2‐dithocarboxylate (catalyst I) has been proposed by reliable computations performed within the formalism of density functional theory. The mechanism of the proposed reaction is similar to the cycloaddition of tertiary aziridines and carbon dioxide using a recyclable catalyst that is reported to provide access to 3‐substituted 2‐oxazolidones with excellent yield. Because the rate determining step needs to surmount a high energy barrier, the reaction route has been deciphered in high boiling solvent (1, 2‐ethanediol). The highlight of the mechanistic route detailed here is that the proposed pathway is a cyclic process that is exothermic in nature with the regeneration of the catalyst and involves simple reagents. Copyright © 2016 John Wiley & Sons, Ltd.
The importance of regulatory data protection or exclusive use and other forms of intellectual property rights in the crop protection industry
Authors: Carroll Michael J
Published: May 2016

In order for a chemical plant protection product to be authorised for sale a registration dossier has to be assembled to demonstrate safety and efficacy to the satisfaction of government regulators. These studies and tests are protected for a period of 10 years in Europe, North America and some other jurisdictions from the date of first product authorisation so that only the data owner can gain commercial benefit from the data. Subsequent regulatory reviews which require new studies should not result in further periods of regulatory data protection exclusive use for the new data but compensation should be payable to the data generator. © 2016 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.
Computational design of two‐phase auxetic structures
Authors: Strek Tomasz , Jopek Hubert , Idczak Eligiusz
Published: May 2016

Optimization of structures with complex shapes is a big challenge for computational physics. Results of numerical calculations show that composite or sandwich panel structures have a great influence on their effective properties. This article presents numerical results of optimization of sandwich panel properties. Calculations were provided for a three‐layer sandwich two‐phase composite. Optimization techniques were used for minimization of the effective Poisson's ratio of the core. The resultant composite structure exhibits a negative Poisson's ratio (NPR), although all its constituents are characterized by positive values of the Poisson's ratio. The structure of the composite is completely filled with solid materials, hence no voids appear within its whole volume. To find a solution, the finite‐element method combined with an optimization algorithm MMA (method of moving asymptotes) was used. For the purpose of analysis, the material parameters were written by means of the shape interpolation SIMP (solid isotropic material with penalization) scheme.
The nature of boron‐oxygen lifetime‐degrading centres in silicon
Authors: Voronkov Vladimir , Falster Robert
Published: May 2016

Light‐induced degradation of minority carrier lifetime in silicon is caused by the formation of two B‐O recombination centres: fast‐stage centres (FRC) and slow‐stage centres (SRC). FRC were concluded to emerge by a carrier‐assisted reconfiguration of a latent BO2 defect composed of a substitutional boron atom and an oxygen dimer. The nature of SRC however remained uncertain; this defect appeared to involve an interstitial boron atom rather than a substitutional one. More recent data on SRC in boron‐containing compensated p‐Si and n‐Si now show that the SRC actually emerge in the same way as FRC: by a reconfiguration of BO2, but from a different latent form. The two latent BO2 defects (the precursors for FRC and for SRC) are created during a cooling stage after the last high‐temperature anneal, and their concentration, proportional to the boron concentration and squared oxygen concentration, depends on the cooling rate. (© 2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Rapid point‐of‐care identification of oral medications in gastric lavage content by ambient mass spectrometry in the emergency room
Authors: Lee Chi‐Wei , Su Hung , Wu Kun‐Da , Shiea Jentaie , Wu Deng‐Chyang , Chen Bai‐Hsiun , Shin Shyi‐Jang
Published: May 2016

Rationale

Acute poisoning should be handled with high efficiency in order to minimize morbidity and mortality in the emergency room. Unfortunately, history‐taking and physical examination are not always reliable. Mis‐swallowing of oral medications is common in the pediatric group. This study aimed at developing a rapid point‐of‐care ambient mass spectrometric method for the early identification of ingested oral medications in gastric lavage content.

Methods

Four different types of oral medications that are most commonly mis‐swallowed by children were diluted to different concentrations. Each of these chemical solutions was mixed with human gastric lavage content. A direct metallic sampling probe was dipped into the solution. It was then inserted promptly into the thermal desorption electrospray ionization source to carry out ionization and subsequent mass spectrometric analysis of the medications. The corresponding compounds were identified through matching of the obtained mass spectrometric data with those provided by well‐established databases.

Results

Since no pretreatment of the specimen was required, the sampling step, and the subsequent thermal desorption electrospray ionization and mass spectrometric detection of the medications were completed within 30 s. Mass spectra were obtained for four different kinds of oral medication. The limit‐of‐detection of the four tested oral medications in gastric lavage content is at sub‐ppm level, which is sensitive enough for emergency medicine applications since the quantities of medications ingested by pediatric patients are usually much higher.

Conclusions

Thermal desorption electrospray ionization mass spectrometry, with informational support provided by an online mass spectral database, allows for early point‐of‐care identification of mis‐swallowed oral medications in the evacuated gastric lavage contents obtained from gastric lavage of patients in the emergency room, and it is promising in providing important toxicological information to ensure the appropriateness of the subsequent medical management. Copyright © 2016 John Wiley & Sons, Ltd.
Use of deuterium labeling by high‐temperature solid‐state hydrogen‐exchange reaction for mass spectrometric analysis of bradykinin biotransformation
Authors: Kopylov Arthur T. , Myasoedov Nikolay F. , Dadayan Alexander K. , Zgoda Victor G. , Medvedev Alexei E. , Zolotarev Yurii A.
Published: May 2016

Rationale

Studies of molecular biodegradation by mass spectrometry often require synthetic compounds labeled with stable isotopes as internal standards. However, labeling is very expensive especially when a large number of compounds are needed for analysis of biotransformation. Here we describe an approach for qualitative and quantitative analysis using bradykinin (BK) and its in vitro degradation metabolites as an example. Its novelty lies in the use of deuterated peptides which are obtained by a high‐temperature solid‐state exchange (HSCIE) reaction.

Methods

Deuterated and native BK were analyzed by positive electrospray ionization high‐resolution mass spectrometry (ESI‐HRMS) using an Orbitrap Fusion mass spectrometer. High‐energy collision‐induced dissociation (HCD) experiments were performed on [M+H]+ and [M+2H]2+ ions in targeted‐MS2 mode with adjusted normalized HCD value.

Results

After the HSCIE reaction, each amino acid residue of the deuterated peptide contained deuterium atoms and the average degree of substitution was 5.5 atoms per the peptide molecule. The deuterated peptide demonstrated the same chromatographic mobility as the unlabeled counterpart, and lack of racemization during substitution with deuterium. Deuterium‐labeled and unlabeled BKs were incubated with human plasma and their corresponding fragments BK(1‐5) and BK(1‐7), well known as the major metabolites, were detected.

Conclusions

Quantitative assays demonstrated applicability of the heavy peptide for both sequencing and quantification of generated fragments. Applicability of the HSCIE deuterated peptide for analysis of routes of its degradation has been shown in in vitro experiments. Copyright © 2016 John Wiley & Sons, Ltd.
Molecular recognition of emerald ash borer infestation using leaf spray mass spectrometry
Authors: Falcone Caitlin E. , Cooks R. Graham
Published: May 2016

Rationale

The introduction of the emerald ash borer (Agrilus planipennis) (EAB) from Asia to Michigan, USA, in the 1990s caused the widespread death of ash trees in two Canadian provinces and 24 US states. The three current methods for the detection of emerald ash borer infestation, visual surveys, tree girdling and artificial traps, can be unreliable, and there is clearly a need for a rapid, dependable technique for the detection of emerald ash borer infestation.

Methods

Leaf spray, an ambient ionization method for mass spectrometry (MS), gives direct chemical information on a leaf sample by applying a high voltage to a naturally or artificially sharply pointed leaf piece causing ions to be generated directly from the leaf tip for MS analysis.

Results

Leaflets from 23 healthy and EAB‐infested ash trees were analyzed by leaf spray mass spectrometry in an attempt to distinguish healthy and EAB‐infested ash trees. In negative ion mode, healthy ash trees showed an increased abundance of ionsm/z455.5, 471.5 and 487.5, and ash trees infested with the EAB displayed an increased abundance of ionsm/z181 and 217. The identities of the chemical discriminators ursolic acid and oleanolic acid in healthy ash trees, and six‐carbon sugar alcohols in infested ash trees, were determined by tandem mass spectrometry and confirmed with standards.

Conclusions

This preliminary study suggests that leaf spray mass spectrometry of ash tree leaflets provides a potential tool for the early detection of ash tree infestation by the emerald ash borer. Copyright © 2016 John Wiley & Sons, Ltd.
Analysis of argentinated peptide complexes using matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry: Peptide = oxytocin, arg8‐vasopressin, bradykinin, bombesin, somatostatin, neurotensin
Authors: Gupta Shyam L. , Dhiman Vikas , Jayasekharan T. , Sahoo N. K.
Published: May 2016

Rationale

The increased use of silver nanoparticles (AgNPs) for various biological applications, and over‐expression of various peptide receptors in different tumors/cancer cells, necessitate the need for dedicated investigations on the intrinsic binding ability of Ag with various biologically important peptides for better understanding of AgNPs‐peptide interactions and for the future development of contrasting agents as well as drugs for imaging/biomedical applications.

Methods

The [M+(Ag)n]+ complexes are prepared and characterized using matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOFMS).

Results

Silver complexes of the peptides [M+(Ag)n]+, where M = oxytocin, arg8‐vasopressin, bradykinin, bombesin, somatostatin, and neurotensin, have been investigated for their intrinsic Ag+‐binding ability. Unusual binding of up to seven Ag+ with these small peptides is observed. The mass spectra show n = 1–5 for bombesin and somatostatin, n = 1–6 for bradykinin and arg8‐vasopressin, and n = 1–7 for oxytocin and neurotensin. In addition, oxytocin and arg8‐vasopressin show the formation of dimers and their complexes [M2+(Ag)n]+ with n = 1–8 and n = 1–5, respectively. The possible amino acid residues responsible for Ag+ binding in each peptide have been identified on the basis of density functional theory (DFT)‐calculated binding energy values of Ag+ towards individual amino acids.

Conclusions

Mass spectrometric evidence indicates that the peptides, viz., oxytocin, arg8‐vasopressin, bradykinin, bombesin, somatostatin, and neurotensin, show greater affinity for Ag+. Hence, they may be used as carriers for AgNPs in targeted drug delivery as well as an alternative for iodinated contrasting agents in dual energy X‐ray imaging techniques. Radio‐labeled Ag with these peptides can also be used in radio‐pharmaceuticals for diagnostic and therapeutic applications. Copyright © 2016 John Wiley & Sons, Ltd.
Liquid chromatography/mass spectrometry identification of intermediates and vulcanization products by using squalene as vulcanization model compound
Authors: Giansanti Luisa , Aleandri Simone , Altieri Barbara , Caretti Fulvia , Mancini Giovanna , Morosetti Stefano , Ventura Salvatore , Pérez‐Fernández Virginia , Gentili Alessandra
Published: May 2016

Rationale

Sulfur‐vulcanized rubber is a three‐dimensional polymer network, insoluble in all organic solvents. For this reason, vulcanization products are difficult to study and identify by conventional analytical techniques. To simplify this task, low molecular weight olefins have been used as model compounds (MCs) in place of rubber in vulcanization experiments.

Methods

In this work, the vulcanization process was investigated using squalene (SQ) as MC. By‐products, intermediates and products were separated by semipreparative reversed‐phase liquid chromatography (RPLC) with UV detection. Each fraction was collected, concentrated and characterized by flow injection analysis (FIA) and non‐aqueous reversed‐phase (NARP) LC coupled to positive atmospheric pressure chemical ionization mass spectrometry (APCI‐MS). Under the latter conditions, an Information‐Dependent Acquisition (IDA) was performed on a linear ion trap mass spectrometer to obtain structural information.

Results

Several vulcanized compounds containing up to three SQ molecules, cross‐linked with chains involving up to 14 sulfur atoms overall, have been identified along with some of their oxidized products (epoxides and hydroperoxides). The FIA‐MS spectra showed peak clusters, each of which included two‐three subclusters; the interpretation was complicated by the occurrence of more ion species per product, by the unsaturation grade and by the characteristic isotopic distribution of sulfur. The enhanced product ion scan (EPI) spectra, acquired during the IDA experiments, supported the FIA‐MS identification allowing one to count the number of sulfur atoms.

Conclusions

The sensitivity of the developed analytical strategy was due to the enrichment factor achieved via semipreparative chromatography and the very good response of the APCI detection. Pattern fragmentation and chromatographic behavior simplified the identification of the cured compounds and their oxidized products, whose occurrence was related to the grade of oxidation of SQ used as reagent. Copyright © 2016 John Wiley & Sons, Ltd.
Threonine versus isothreonine in synthetic peptides analyzed by high‐resolution liquid chromatography/tandem mass spectrometry
Authors: Kuznetsova Ksenia G. , Trufanov Pavel V. , Moysa Alexander A. , Pyatnitskiy Mikhail A. , Zgoda Viktor G. , Gorshkov Mikhail V. , Moshkovskii Sergei A.
Published: May 2016

Rationale

One of the problems in proteogenomic research aimed at identification of variant peptides is the presence of peptides with amino acid isomers of different origin in the analyzed samples. Among the most challenging examples are peptides with threonine and isothreonine (homoserine) in their sequences. Indeed, the latter residue may appear in vitro as a methionine substitution during sample preparation for shotgun proteome analysis. Yet, this substitution of Met to isoThr is not encoded genetically and should be unambiguously distinguished from, e.g., point mutations in proteins that result in Met conversion to Thr.

Methods

In this work we compared tandem mass (MS/MS) spectra produced by an Orbitrap mass spectrometer of Thr‐ and isoThr‐containing tryptic peptides and found a distinctive feature in their collisionally activated fragmentation patterns.

Results

Up to 84% of MS/MS spectra for peptides containing isoThr residues have been positively specified. We also studied the differences in retention times for peptides containing Thr isoforms that can be further used for their distinction.

Conclusions

Threonine can be distinguished from isothreonine by its retention time and HCD fragmentation pattern, specifically relative intensity of the bn‐ product ion, which can be further used in proteomic research. Copyright © 2016 John Wiley & Sons, Ltd.
Determination of emerging nitrogenous economic adulterants in milk proteins by high‐performance liquid chromatography/compact mass spectrometry
Authors: Draher Jonathan , Ehling Stefan , Cellar Nick , Reddy Todime , Henion Jack , Sousou Nigel
Published: May 2016

Rationale

Milk‐derived ingredients are widely used around the world in the manufacturing of nutritional products. They are prone to economically motivated adulteration with nitrogenous compounds such as melamine and its analogs in order to increase the nitrogen content of these ingredients. The need to rapidly screen milk‐derived ingredients to detect adulteration is of paramount public health concern. A liquid chromatography/mass spectrometry (LC/MS)‐based method using a single quadrupole mass spectrometer has been developed for the rapid frontline analysis of six nitrogenous protein adulterants, i.e. melamine, ammeline, ammelide, amidinourea, cyromazine and cyanuric acid, in three key milk‐derived ingredients, i.e. whole milk powder, nonfat milk powder and whey protein concentrate.

Methods

The sample preparation scheme involves both 'dilute and shoot' as well as solid‐phase extraction (SPE)‐based methods. The 'dilute and shoot' scheme uses a tenfold dilution of sample with water followed by protein precipitation using 2% formic acid in acetonitrile. The SPE scheme involves tenfold dilution of sample with water, followed by protein precipitation using acetonitrile, and further cleanup through Strata Melamine SPE cartridges. Sample extracts were analyzed by hydrophilic interaction chromatography/single quadrupole mass spectrometry (HILIC/MS) in both positive and negative electrospray ionization mode. Accurate quantitation was achieved using stable isotope labeled internal standards.

Results

A multi‐day method validation study was conducted using three different milk‐derived ingredients. Average accuracies, relative standard deviations (RSD) and method detection limits (MDL) for all analytes in whole milk powder were 65–118%, 7–11% and 0.9–30 mg/kg, using the 'dilute and shoot' extraction procedure. The SPE procedure results were 102‐111%, 5–13%, and 0.4–2.5 mg/kg, respectively, for melamine, ammeline, ammelide and cyromazine only.

Conclusions

A rugged and simple to use analytical method to screen for the presence of nitrogenous economic adulterants in milk‐derived ingredients has been developed for routine frontline use. Copyright © 2016 John Wiley & Sons, Ltd.
Citrate‐Induced Nanocubes: A Re‐Examination of the Role of Citrate as a Shape‐Directing Capping Agent for Ag‐Based Nanostructures
Authors: Hajfathalian Maryam , Gilroy Kyle D. , Hughes Robert A. , Neretina Svetlana
Published: May 2016

Seed‐mediated syntheses utilizing facet‐selective surface passivation provide the necessary chemical controls to direct noble metal nanostructure formation to a predetermined geometry. The foremost protocol for the synthesis of (111)‐faceted Ag octahedra involves the reduction of metal ions onto pre‐existing seeds in the presence of citrate and ascorbic acid. It is generally accepted that the capping of (111) facets with citrate dictates the shape while ascorbic acid acts solely as the reducing agent. Herein, a citrate‐based synthesis is demonstrated in which the presence or absence of ascorbic acid is the shape‐determining factor. Reactions are carried out in which Ag+ ions are reduced onto substrate‐immobilized Ag, Au, Pd, and Pt seeds. Syntheses lacking ascorbic acid, in which citrate acts as both the capping and the reducing agent, result in a robust nanocube growth mode able to withstand wide variations in the concentration of reactants, reaction rates, seed material, seed orientation and faceting, pH, and substrate material. If, however, ascorbic acid is included in these syntheses, then the growth mode reverts to one that advances the octahedral geometry. The implication of these results is that citrate, or one of its oxidation products, selectively caps (100) facets, but where this capability is compromised by ascorbic acid.
Adtpp: lightweight efficient safe polymorphic algebraic data types for C
Authors: Naish Lee , Schachte Peter , MacNally Aleck M.
Published: May 2016

Adtpp is an open‐source tool that adds support for algebraic data types (ADTs) to the C programming language. ADTs allow more precise description of program types and more robust handling of data structures than are directly supported by C. ADT definitions and other declarations are put in a file that is preprocessed by adtpp to produce a C header (‘.h’) file that can be included in C source files. The generated header file contains C type definitions, macros, and inline functions that support type‐safe construction, deconstruction, and pattern matching of ADT values while avoiding unsafe operations such as casts, and avoiding the risk of errors such as dereferencing NULL pointers and accessing inappropriate fields of unions. Values are represented efficiently, using techniques from the implementation of declarative languages. For many simple data types, the memory representation is identical to a direct implementation in C, with no loss of efficiency. For more complex types, the adtpp representation is more efficient than common C representations while preserving type safety and convenience. As an example, we present a new variation of 234‐trees that is very compact. Adtpp also supports parametric polymorphism such as defining a type ‘list of t’, where t can be any ADT, and generic functions such as length. However, polymorphic code is somewhat more verbose than for typical declarative languages, due to our reliance on the limited type checking available in C. Copyright © 2016 John Wiley & Sons, Ltd.