bluuebunny/crossref_metadata_2025 huggingface dataset:
Hydrogen Bonding: Regulator for Nucleophilic Fluorination
Authors: Liang Shengzong , Hammond Gerald B. , Xu Bo
Published: August 2017

The recent advances in nucleophilic fluorination, regulated through hydrogen bonding interactions are summarized. Two main categories of fluorine nucleophiles are discussed. Alkali‐metal fluorides are widely used in various fluorination transformations because they are inexpensive and safe nucleophilic fluorine sources. But the non‐controllable nucleophilicity and strong basicity of some of them cause undesired side reactions, which led to the introduction of hydrogen bonding to fine tune their nucleophilicity and basicity. In contrast, an HF‐based fluorine nucleophile, HF/DMPU, is in some aspects superior to the conventional HF/pyridine (Olah's reagent) or HF/Et3N because of the higher hydrogen bond basicity of DMPU. It has been used in several nucleophilic fluorinations such as fluorination of alkynes, fluoro‐Prins reaction and fluorination of aziridines.
A New, Practical One‐Pot Synthesis of Unprotected Sulfonimidamides by Transfer of Electrophilic NH to Sulfinamides
Authors: Izzo Flavia , Schäfer Martina , Stockman Robert , Lücking Ulrich
Published: August 2017

Unprotected tertiary sulfonimidamides have been prepared in good to excellent yields in a one‐pot transformation from tertiary sulfinamides through NH transfer. The reaction is mediated by commercially available (diacetoxyiodo)benzene and ammonium carbamate in methanol under convenient conditions. A wide range of functional groups are tolerated and initial results indicate that the NH transfer is stereospecific. A small molecule X‐ray analysis of NH sulfonimidamide 2 a and its behavior in selected in vitro assays in comparison to the matched sulfonamide are also reported. This new reaction provides a safe, short and efficient approach to sulfonimidamides, which have been the subject of recent, growing interest in the life sciences.
Psychological distress associated with cancer screening: A systematic review
Authors: Chad‐Friedman Emma , Coleman Sarah , Traeger Lara N. , Pirl William F. , Goldman Roberta , Atlas Steven J. , Park Elyse R.
Published: August 2017

BACKGROUND

Current national cancer screening recommendations include the potential risk of psychological harm related to screening. However, data on the relation of psychological distress to cancer screening is limited. The authors conducted a systematic review to assess psychological distress associated with cancer screening procedures.

METHODS

Studies that administered measures of psychological distress between 2 weeks before and 1 month after the screening procedure were included.

RESULTS

In total, 22 eligible studies met criteria for review, including 13 observational trials and 9 randomized controlled trials. Eligible studies used a broad range of validated and unvalidated measures. Anxiety was the most commonly assessed construct and was measured using the State Trait Anxiety Inventory. Studies included breast, colorectal, prostate, lung, and cervical screening procedures. Distress was low across procedures, with the exception of colorectal screening. Distress did not vary according to the time at which distress was measured. None of the studies were conducted exclusively with the intention of assessing distress at the time of screening.

CONCLUSIONS

Evidence of low distress during the time of cancer screening suggests that distress might not be a widespread barrier to screening among adults who undergo screening. However, more studies are needed using validated measures of distress to further understand the extent to which screening may elicit psychological distress and impede adherence to national screening recommendations. Cancer 2017;123:3882‐94. © 2017 American Cancer Society.
Programmed cell death ligand 1 and tumor‐infiltrating lymphocyte status in patients with renal cell carcinoma and sarcomatoid dedifferentiation
Authors: Kawakami Fumi , Sircar Kanishka , Rodriguez‐Canales Jaime , Fellman Bryan M. , Urbauer Diana L. , Tamboli Pheroze , Tannir Nizar M. , Jonasch Eric , Wistuba Ignacio I. , Wood Christopher G. , Karam Jose A.
Published: August 2017

BACKGROUND

The immune profile of sarcomatoid renal cell carcinoma (sRCC), including the programmed cell death ligand 1 (PD‐L1) and programmed cell death 1 (PD‐1) status, has not been well characterized.

METHODS

An immunohistochemical digital analysis of PD‐L1, PD‐1, CD4, and CD8 was performed on nephrectomy specimens from 118 sRCC patients and 92 nonsarcomatoid clear cell renal cell carcinoma (ccRCC) patients. The clinical characteristics of the population were compared between sRCC and ccRCC. Overall survival was estimated, and comparisons were made between PD‐L1–positive and PD‐L1–negative groups as well as tumor‐infiltrating lymphocyte (TIL)–high and TIL‐low groups.

RESULTS

The PD‐L1 H‐score of sRCC (mean, 3.7; range, 0‐192.1) was significantly higher than the score of grade 4 ccRCC (P = .001), and 41.3% of sRCC cases showed a PD‐L1 H‐score ≥ 10. The PD‐1–positive cell density was significantly higher in sRCC versus ccRCC within the tumor and at the invasive front. The intratumoral CD8‐positive cell density was significantly higher in sRCC versus ccRCC. Forty‐one percent in the sarcomatoid component of sRCC and 8% in the epithelioid component of sRCC had an adaptive immune resistance phenotype (PD‐L1–positive and TIL‐positive), whereas only 1% in ccRCC had the type I phenotype.

CONCLUSIONS

sRCC showed higher PD‐L1 expression and higher PD‐1– and CD8‐positive cell density than grade 4 ccRCC. The results indicate a notable immunosuppressive environment in sRCC. Despite advances in the treatment of advanced‐stage renal cell carcinoma, sRCC still has a poor prognosis. This work describes highly immunosuppressive characteristics of sRCC in comparison with an appropriate ccRCC control. The results suggest PD‐1/PD‐L1 blockade therapy as a potential therapeutic approach for sRCC. Cancer 2017;123:4823‐31. © 2017 American Cancer Society.
Receipt of definitive therapy in elderly patients with unfavorable‐risk prostate cancer
Authors: Yang David D. , Mahal Brandon A. , Muralidhar Vinayak , Boldbaatar Ninjin , Labe Shelby A. , Nezolosky Michelle D. , Vastola Marie E. , Beard Clair J. , Martin Neil E. , Mouw Kent W. , Orio Peter F. , King Martin T. , Nguyen Paul L.
Published: August 2017

BACKGROUND

Conservative management of aggressive prostate cancer in the elderly without definitive therapy has been associated with a 10‐year prostate cancer‐specific mortality of approximately 50%. The authors examined the prevalence of definitive therapy in elderly patients with intermediate‐risk or high‐risk disease.

METHODS

411,343 patients who were diagnosed from 2004 through 2012 with intermediate‐risk or high‐risk prostate cancer were identified in the National Cancer Database. Multivariable logistic regression adjusting for sociodemographic characteristics and comorbidity was used to examine the association between age and receipt of definitive therapy, defined as radical prostatectomy or radiotherapy, and of primary androgen deprivation therapy (ADT) among patients who did not receive definitive therapy.

RESULTS

In total, 87.1% of high‐risk patients and 91.9% of intermediate‐risk patients received definitive therapy. When stratified by age, 93.7%, 92.1%, 90.8%, 87.6%, 80.9%, and 55.2% of high‐risk patients and 96.1%, 94.7%, 93.4%, 89.7%, 82.7%, and 62.8% of intermediate‐risk patients ages <60, 60 to 64, 65 to 69, 70 to 74, 75 to 79, and ≥80 years received definitive therapy, respectively. For both high‐risk and intermediate‐risk patients, increasing age was significantly associated with a decreased likelihood of receiving definitive therapy overall (both P < .001) and a greater likelihood of receiving primary ADT among those who did not receive definitive therapy (both P < .001).

CONCLUSIONS

Older age was significantly associated with a decreased likelihood of receiving definitive therapy and an increased likelihood of receiving primary ADT in this national cohort of patients with intermediate‐risk or high‐risk prostate cancer. Notably, approximately 40% to 45% of patients aged ≥80 years did not receive definitive therapy. These findings are alarming given the dismal outcomes of conservatively managed unfavorable‐risk prostate cancer. Cancer 2017;123:4832‐40. © 2017 American Cancer Society.
An Experimental Radical Electrophilicity Index
Authors: Santschi Nico , Nauser Thomas
Published: August 2017

We present an experimental electrophilicity index (ϻ) for the classification of radicals. The ϻ‐scale is based on the equilibrium constant determined for the reversible addition of a radical R. to an aromatic radicophile (HisNH2). This experimental approach is in excellent agreement with the computed global electrophilicity index ω and serves to validate the latter.
Genetic diversity and sex‐bias dispersal of plateau pika in Tibetan plateau
Authors: Zhang Liangzhi , Qu Jiapeng , Li Kexin , Li Wenjing , Yang Min , Zhang Yanming
Published: August 2017

Dispersal is an important aspect in organism's life history which could influence the rate and outcome of evolution of organism. Plateau pika is the keystone species in community of grasslands in Tibetan Plateau. In this study, we combine genetic and field data to character the population genetic pattern and dispersal dynamics in plateau pika (Ochotona curzoniae). Totally, 1,352 individual samples were collected, and 10 microsatellite loci were analyzed. Results revealed that plateau pika possessed high genetic diversity and inbreeding coefficient in a fine‐scale population. Dispersal distance is short and restricted in about 20 m. An effective sex‐biased dispersal strategy is employed by plateau pika: males disperse in breeding period for mating while females do it after reproduction for offspring and resource. Inbreeding avoiding was shown as the common driving force of dispersal, together with the other two factors, environment and resource. In addition, natal dispersal is female biased. More detailed genetic analyzes are needed to confirm the role of inbreeding avoidance and resource competition as ultimate cause of dispersal patterns in plateau pika.
Prevalence and genetic diversity of Batrachochytrium dendrobatidis in Central African island and continental amphibian communities
Authors: Hydeman Marina E. , Longo Ana V. , Velo‐Antón Guillermo , Rodriguez David , Zamudio Kelly R. , Bell Rayna C.
Published: August 2017

The fungal pathogen Batrachochytrium dendrobatidis (Bd) infects hundreds of amphibian species and is implicated in global amphibian declines. Bd is comprised of several lineages that differ in pathogenicity, thus, identifying which Bd strains are present in a given amphibian community is essential for understanding host–pathogen dynamics. The presence of Bd has been confirmed in Central Africa, yet vast expanses of this region have not yet been surveyed for Bd prevalence, and the genetic diversity of Bd is largely unknown in this part of the world. Using retrospective surveys of museum specimens and contemporary field surveys, we estimated the prevalence of Bd in Central African island and continental amphibian assemblages, and genotyped strains of Bd present in each community. Our sampling of museum specimens included just a few individuals collected in the Gulf of Guinea archipelago prior to 1998, yet one of these individuals was Bd‐positive indicating that the pathogen has been on Bioko Island since 1966. We detected Bd across all subsequent sample years in our study and found modest support for a relationship between host life history and Bd prevalence, a positive relationship between prevalence and host community species richness, and no significant relationship between elevation and prevalence. The Global Panzootic Lineage (BdGPL) was present in all the island and continental amphibian communities we surveyed. Our results are consistent with a long‐term and widespread distribution of Bd in amphibian communities of Gabon and the Gulf of Guinea archipelago.
Facile Deboronation of Some o‐Carboranylamides
Authors: Nie Yong , Wang Yafeng , Miao Jinling , Hu Chunhua , Zhang Zhenwei , Cui Yu , Li Yexin
Published: August 2017

The crystal structures of the known closo‐carboranylamide 1,2‐(PhNHCO)2‐o‐C2B10H10 (3) as diethyl ether and toluene/water solvates are reported. Compound 3 undergoes gradual deboronation in wet diethyl ether leading to the corresponding nido‐carboranylamide [PhNH3][7,8‐(PhNHCO)2‐nido‐C2B9H10] (4). The structure of 4 has been confirmed by X‐ray crystal structure analysis. Further experimental and theoretical evidence shows that the presence of the electron‐withdrawing amide moieties facilitates the deboronation of these closo‐carboranylamides in certain solvents affording the corresponding nido‐carboranylamides.
Lanthanide Tetrafluoroterephthalates for Luminescent Ink‐Jet Printing
Authors: Utochnikova Valentina V. , Grishko Alexey , Vashchenko Andrey , Goloveshkin Alexander , Averin Aleksey , Kuzmina Natalia
Published: August 2017

Lanthanide tetrafluoroterephthalates, Ln2ftp3·6H2O (Ln = Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb), (EuxTb1–x)2ftp3·6H2O, and (EuxTb1–x)2ftp3(Phen)2·2H2O (Phen = o‐phenanthroline) were obtained for the first time and studied in detail. Water solutions of the terbium and europium tetrafluoroterephthalates were for the first time successfully used for ink‐jet security luminescent printing.
Synthesis of (±)‐Pregabalin by Utilizing a Three‐Step Sequential‐Flow System with Heterogeneous Catalysts
Authors: Ishitani Haruro , Kanai Kan , Saito Yuki , Tsubogo Tetsu , Kobayashi Shū
Published: August 2017

(±)‐Pregabalin, a γ‐amino acid derivative, has been synthesized by utilizing flow methods. A three‐step sequential‐flow reaction starting from commercial isovaleraldehyde and methyl malonate proceeded smoothly with heterogeneous catalysts to afford the precursor of pregabalin in yields of 75–100 %, and a space‐time yield of 52.2 g/L d was reached. In addition, a heterogeneous catalyst for the Knoevenagel reactions of aldehydes with malonates, which is the first step of the synthesis, has been developed. Pregabalin was finally obtained by acid‐catalyzed hydrolysis of the precursor followed by neutralization.
Highly Efficient and Chemoselective Tertiary and Secondary Benzylation of Thiols Catalyzed by Indium(III) Triflate
Authors: Kuciński Krzysztof , Hreczycho Grzegorz
Published: August 2017

Several examples of nucleophilic substitution reactions of compounds that have good leaving groups have been previously reported, but the direct use of simple alcohols still remains a challenge because of the poor leaving ability of the hydroxy group. Herein, an efficient and highly chemoselective method for the S‐benzylation of a wide range of aromatic and aliphatic thiols has been accomplished in the presence of catalytic amounts (0.1–0.2 mol‐%) of indium(III) triflate. Our approach is atom efficient (water is the only byproduct) and suitable to obtain the corresponding unsymmetrical thioethers in excellent yields (up to 99 %). The low loading of catalyst that are needed to obtain extraordinarily high chemoselectivities and the generality of the reaction make this approach unique.
Affinity chromatography on monolithic supports for simultaneous and high‐throughput isolation of immunoglobulins from human serum
Authors: Martinović Tamara , Andjelković Uroš , Klobučar Marko , Černigoj Urh , Vidič Jana , Lučić Marina , Pavelić Krešimir , Josić Djuro
Published: August 2017

Posttranslational modifications of immunoglobulins have been a topic of great interest and have been repeatedly reported as a major factor in disease pathology. Cost‐effective, reproducible, and high‐throughput (HTP) isolation of immunoglobulins from human serum is vital for studying the changes in protein structure and the following understanding of disease development. Although there are many methods for the isolation of specific immunoglobulin classes, only a few of them are applicable for isolation of all subtypes and variants. Here, we present the development of a scheme for fast and simultaneous affinity purification of α (A), γ (G), and μ (M) immunoglobulins from human serum through affinity monolith chromatography. Affinity‐based monolithic columns with immobilized protein A, G, or L were used for antibody isolation. Monolithic stationary phases have a high surface accessibility of binding sites, large flow‐through channels, and can be operated at high flow rates, making them the ideal supports for HTP isolation of biopolymers. The presented method can be used for HTP screening of human serum in order to simultaneously isolate all three above‐mentioned immunoglobulins and determine their concentration and changes in their glycosylation pattern as potential prognostic and diagnostic disease biomarkers.
Durable Flexible Supercapacitors Utilizing the Multifunctional Role of Ionic Liquids
Authors: Lorenzo Marta , Srinivasan Geetha
Published: August 2017

A simple scalable approach to design flexible, ultrathin, and safe supercapacitors to power up the next‐generation of portable electronics and implantable biomedical devices is reported. The main challenge to construct flexible supercapacitors is the development of flexible electrodes that can retain characteristics of high power density, long cycle life, and high efficiency during and after bending. In this work, flexible electrodes based on conducting polymer–biopolymer–ionic liquid–graphite composites that are chemically blended and stable have been prepared. They are used as electrodes in the fabrication of three devices, that is, (i) electrochemical, (ii) electrical double‐layer, and (iii) hybrid supercapacitors. The multifunctional role of ionic liquids as solvent, electrolyte, and plasticizer is exploited to fabricate these innovative supercapacitors. These flexible supercapacitors show specific capacitances of around 5 mF g−1, an operational voltage of about 2.2 V, and an excellent cycle life of >15 000 cycles with nearly 100 % efficiency. The design nature of these electrodes, chemical stability, and feasibility to use biocompatible components will enable the construction of task‐specific supercapacitors with excellent device stability.
Physicochemical treatment for improving bioconversion of cassava industrial residues
Authors: Sudha A. , Sivakumar V. , Sangeetha V. , Priyenka Devi K.S.
Published: August 2017

In the present study, a comparison of two types of microwave pretreatment such as microwave assisted alkali and microwave assisted acid were studied using cassava pulp as the substrate. The effect of pretreatment agent concentration, microwave power and pretreatment time on enzymatic saccharification was studied using a response surface method according to Central Composite design. Under optimized conditions, microwave assisted alkali pretreatment of cassava pulp with 2.27% NaOH at 125 W for 18 min followed by enzymatic hydrolysis gave reducing sugar yield of 0.472 g g−1 dry biomass, while microwave assisted acid treatment with 1.95% H2SO4 at 135 W for 25 min showed reducing sugar yield of 0.306 g g−1 dry biomass. The yield from microwave assisted alkali was higher and was 2.7 times higher than that obtained with raw cassava pulp. Microwave assisted liquefaction of pretreated cassava pulp at 100 W for 30 min using amylase lowered the process time. © 2017 American Institute of Chemical Engineers Environ Prog, 37: 577–583, 2018
Increased N200 and P300 latencies in cognitively impaired elderly carrying ApoE ε‐4 allele
Authors: Cintra Marco Túlio Gualberto , Ávila Rafaela Teixeira , Soares Thayana Oliveira , Cunha Luciana Cristina Matos , Silveira Katia Daniela , de Moraes Edgar Nunes , Simas Kaique Roger , Fernandes Renato Bragança , Gonçalves Denise Utsch , de Rezende Nilton Alves , Bicalho Maria Aparecida Camargos
Published: August 2017

Objective

To compare the results of neuropsychological tests, evoked potentials N200 and P300 and polymorphisms of ApoE and BDNF rs6265 between patients with normal cognition and those with mild cognitive impairment (MCI) and Alzheimer's dementia (AD).

Methods

This is a cross‐sectional study of elderly individuals with normal cognition and those with MCI and AD, who were submitted to evoked potential tests (N200 and P300) by means of hearing stimuli based on the auditory oddball paradigm. Genotyping was obtained by using the real‐time PCR technique.

Results

Sixty‐five patients were evaluated as follows: 14 controls, 34 with MCI and 17 with AD. N200 latency and P300 latency and amplitude were not associated with MCI and AD diagnosis. Patients with cognitive impairment (MCI or AD) showed increase in the latencies of P300 and N200. BNDF gene was not associated with cognitive impairment.

Conclusion

Latencies of N200 and P300 increased in cognitively impaired patients with the presence of ApoE ε‐4 allele.
Engaging hepatitis C infected patients in cost‐effectiveness analyses: A literature review
Authors: Mattingly T. Joseph , Perfetto Eleanor M. , Johnson Sophia L.
Published: August 2017

Cost‐effectiveness analyses (CEAs) of hepatitis C virus (HCV) treatment strategies have become common, but few appear to include patient engagement or the patient perspective. The objectives of the current study were to (1) identify published HCV CEA studies that include patient input and (2) derive insights on patient‐informed variable and outcome selection to build a framework for future economic analyses of HCV. A literature search was conducted using SCOPUS, EMBASE, and PubMed from January 1, 2012 to May 28, 2017. Terms sought included a combination of “incremental cost‐effectiveness ratio” OR “economic evaluation” OR “cost effectiveness analysis” OR “cost utility analysis” OR “budget impact analysis” OR “cost benefit analysis” AND “hepatitis C”. A total of 1,040 articles were identified in the search and seven articles were selected for further evaluation after abstracts and the full text of eligible articles were screened. One economic evaluation used direct patient engagement to account for patient preferences in the final model. The study endpoints identified included a variety of clinical, social, psychological, and economic outcomes. Costs primarily focused on productivity loss, missed work, out‐of‐pocket treatment costs, and indirect costs to family or friends supporting the patient. Conclusion: To date, the inclusion of the patient voice through patient engagement as part of methods in cost‐effectiveness research in existing published studies has been limited. Future CEA studies should consider how patient engagement may impact economic models and their implementation into practice. (Hepatology 2018;67:774‐781).
Immunohistochemical expression of cereblon and MUM1 as potential predictive markers of response to lenalidomide in extranodal marginal zone B‐cell lymphoma of the mucosa‐associated lymphoid tissue (MALT lymphoma)
Authors: Kiesewetter Barbara , Simonitsch‐Klupp Ingrid , Kornauth Christoph , Dolak Werner , Lukas Julius , Mayerhoefer Marius E. , Raderer Markus
Published: August 2017

Lenalidomide is an active agent for the treatment of MALT lymphoma. Recently, high expression levels of cereblon (CRBN) and MUM1 have been associated with better response rates in multiple myeloma treated with lenalidomide. However, there are no data on CRBN and MUM1 expression in MALT lymphoma. In the current study, we have systematically investigated a potential correlation of CRBN/MUM1 immunohistochemical expression and response to lenalidomide‐based therapy in a series of 46 patients with MALT lymphoma treated at the Medical University Vienna 2009 to 2014. In total, 28% (13/46) of biopsy specimens derived from gastric tissues, while 72% (33/46) originated from extragastric MALT lymphoma. In terms of CRBN, 54% showed high expression (CRBN+, ≥50% positive cells); the remaining 46% were classified as low expression (CRBN−). In contrast to other reports, there was a non‐significant trend towards worse response rates in CRBN+ (68% versus 86%, P = 0.161). Relapse rates (P = 0.592) and PFS (P = 0.306) did not differ between CRBN+/CRBN−, but all 3 patients progressing on lenalidomide were CRBN+ and both patients completely lacking CRBN expression responded to treatment. Concerning MUM1, 62% were MUM1‐negative (MUM1−) and 38% positive (MUM1+). There was no difference in response to lenalidomide by MUM1‐status (MUM1+ 71% versus MUM1− 79%, P = 0.546) and also relapse rates (P = 0.828) and PFS (P = 0.681) did not differ. Interestingly, a subgroup analysis of gastric lymphoma revealed a significantly better PFS for CRBN− and MUM1− patients, respectively (both P < 0.05). To conclude, there was no significant difference in response to lenalidomide between patients with low or high expression of CRBN/MUM1 in a general population of MALT lymphoma, and immunohistochemical CRBN/MUM1 assessment cannot be recommended in the clinical routine.
Low folate metabolic stress reprograms DNA methylation‐activated sonic hedgehog signaling to mediate cancer stem cell‐like signatures and invasive tumour stage‐specific malignancy of human colorectal cancers
Authors: Feng Hsin‐Chun , Lin Jhuan‐Yu , Hsu Shu‐Han , Lan Wen‐Yu , Kuo Chang‐Sheng , Tian Yu‐Feng , Sun Ding‐Ping , Huang Rwei‐Fen Syu
Published: August 2017

The mechanistic role of colonic low folate metabolic stress (LFMS) in colorectal cancer (CRC) malignancy development remains unknown. Folate analysis on the 99 paired human CRC tissues localized LFMS to the deep invasive T3/T4 staged tumours with hypo‐methylated sonic hedgehog (Shh) promoter region and amplified expressions of Shh ligand and Gli1 effector, which coincided with deregulated expressions of the epithelial‐mesenchymal transition (EMT) mediators. Colonic folate levels of CRC were inversely correlated with pluripotent expressions of the SOX2, NANOG and OCT4 markers (p < 0.05). Exposure of human colon adenocarcinoma cells to LFMS microenvironment significantly hypomethylated Shh promoter region, activated Shh signaling, induced transcript and protein expressions of the pluripotent markers, promoted trans‐differentiation as EMT by deregulation of Snail mediator and epithelial marker E‐cadherin, increased MMP2/MMP9 enzymatic digestion on matrix protein for invasion, and promoted self‐renewal capability of anchorage‐independent tumor‐spheroid formation. LFMS‐induced cancer stem cell (CSC) signature and CRC invasion is synergized with inhibition of DNA methylation by 5‐Aza‐2‐deoxycytidine (5AZA) in rewiring EMT genotypes, which can be blockade by the Shh inhibitor (cyclopamine). The in vivo and in vitro data corroboratively identify CSC‐like molecular targets specific to the LFMS‐predisposed invasive CRC through reprogramming DNA methylation‐activated Shh signaling. The study highlights CSC targets specific to LFMS‐predisposed invasive CRC in optimizing folate co‐chemotherapy to minimize tumour metastasis potential of CRC patients.
Asymmetric Transfer Hydrogenation of Ketones Using New Iron(II) (P‐NH‐N‐P′) Catalysts: Changing the Steric and Electronic Properties at Phosphorus P′
Authors: Smith Samantha A. M. , Prokopchuk Demyan E. , Morris Robert H.
Published: August 2017

The asymmetric transfer hydrogenation (ATH) of ketones is an efficient method for producing enantio‐enriched alcohols which are used as intermediates in a variety of industrial processes. Here we report the synthesis of new iron ATH precatalysts (S,S)‐[FeBr(CO)(Ph2PCH2CH2NHCHPhCHPhNC=CHCH2PR′2)][BPh4] (R′=Et, and ortho‐tolyl (o‐Tol)) where one of the phosphine groups is modified with small alkyl and large aryl substituents to probe the effect of this change on the activity and selectivity of the catalytic system. A simple reversible equilibrium kinetic model is used to obtain the initial TOF and the inherent enantioselectivity S=kR/kS of these catalysts along with those for the previously reported catalysts with R′=Ph and Cy for the ATH of acetophenone. With an increase in the size of the PR′2 group, the TOF goes through a maximum at PPh2 while the S value goes through a maximum of 510 at R′=Cy. The complex with R′=o‐Tol starts with a high S value of 200 but is rapidly changed to a second catalyst with an S value of 28. For the reduction of acetophenone to (R)‐1‐phenylethanol, turnover numbers of up to 5200 and ee up to 98 % were achieved. The chemotherapeutic pharmaceutical precursor (R)‐(3′,5′‐bis(trifluoromethyl))‐1‐phenylethanol is synthesized in up to 95 % ee. Several other alcohols can be prepared in greater than 90 % ee by choosing the precatalyst with the correctly matched steric properties. A hydride complex derived from the catalyst with R′=Cy is characterized by NMR spectroscopy. It is proposed that low concentration trans‐hydride carbonyl complexes with the FeH parallel to the NH of the ligand are the active catalysts in all of these systems.
Mononuclear cell collection for extracorporeal photopheresis: Concentrate characteristics for off‐line UV‐A irradiation procedure
Authors: Piccirillo Nicola , Putzulu Rossana , Massini Giuseppina , Fiore Assunta Gessica , Chiusolo Patrizia , Sica Simona , Zini Gina
Published: August 2017

Background and objective

Extracorporeal photopheresis (ECP) is the most represented cell therapy for treatment of cutaneous T‐cell lymphoma, graft‐versus host disease and organ rejection. We analyzed our experience in ECP using 2 cell separators (Cobe Spectra and Spectra Optia) focusing on leukapheretic product characteristics, UV‐A irradiation procedure and entire ECP process.

Materials and methods

We collected data of patients undergoing ECP between January 2012 and February 2015 in order to evaluate collection procedures performed using Cobe Spectra and Spectra Optia, mononuclear cell product, UV‐A photoirradiation procedure by Pit System.

Results

We performed 484 ECP procedures in 27 patients. Cobe‐derived mononuclear cell products were characterized by higher cell yields while Optia‐derived mononuclear cell products were characterized by smaller volume, comparable mononuclear cell content but lower erythrocytes, granulocytes, and platelets contamination.

Conclusion

Our study confirms good results for both cell separators. Blood volume processed being equal, Cobe collects a number of total nucleated cells significantly higher than Optia. Optia, collecting only target cells without significant erythrocytes, granulocytes and platelets contamination, is able to collect a leukapheretic product particularly suitable for ECP.
Noncovalent interactions between cisplatin and graphene prototypes
Authors: Cuevas‐Flores Ma del Refugio , Garcia‐Revilla Marco Antonio , Bartolomei Massimiliano
Published: August 2017

Cisplatin (CP) has been widely used as an anticancer drug for more than 30 years despite severe side effects due to its low bioavailability and poor specificity. For this reason, it is paramount to study and design novel nanomaterials to be used as vectors capable to effectively deliver the drug to the biological target. The CP square‐planar geometry, together with its low water solubility, suggests that it could be possibly easily adsorbed on 2D graphene nanostructures through the interaction with the related highly conjugated π‐electron system. In this work, pyrene has been first selected as the minimum approximation to the graphene plane, which allows to properly study the noncovalent interactions determining the CP adsorption. In particular, electronic structure calculations at the MP2C and DFT‐SAPT levels of theory have allowed to obtain benchmark interaction energies for some limiting configurations of the CP–pyrene complex, as well as to assess the role of the different contributions to the total interaction: it has been found that the parallel configurations of the aggregate are mainly stabilized around the minimum region by dispersion, in a similar way as for complexes bonded through π‐π interactions. Then, the benchmark interaction energies have been used to test corresponding estimations obtained within the less expensive DFT to validate an optimal exchange‐correlation functional which includes corrections to take properly into account for the dispersion contribution. Reliable DFT interaction energies have been therefore obtained for CP adsorbed on graphene prototypes of increasing size, ranging from coronene, ovalene, and up to C150H30. Finally, DFT geometry optimizations and frequency calculations have also allowed a reliable estimation of the adsorption enthalpy of CP on graphene, which is found particularly favorable (about −20 kcal/mol at 298 K and 1 bar) being twice that estimated for the corresponding benzene adsorption. © 2017 Wiley Periodicals, Inc.
Suitability of pyrolusite as additive to activated coke for low‐temperature NO removal
Authors: Yang Lin , Jiang Wenju , Yao Lu , Jiang Xia , Li Jianjun
Published: August 2017

BACKGROUND

Pyrolusite was used as additive to prepare coal‐based activated coke (AC) for low‐temperature NO removal. The pyrolusite modified AC was prepared by a blending method, and the denitrification performance was evaluated in a lab‐scale simulated fixed‐bed reactor.

RESULTS

The blending of pyrolusite promoted the specific surface area and pore structure of AC, even though the MnO2 and Fe2O3 showed inhibitory effects when blended separately. Both the basic and acid sites of AC‐Mn(x) increased owing to the participation of the blended MnO2 during the activation, while the blending of Fe2O3 showed an inhibited effect. AC‐P10 showed the highest NO removal efficiency at 74.2%, which was 32.8%, 27.0% and 24.2% higher than that of AC, AC‐Mn4 and AC‐Fe6. The operating temperature adaptability and stability of catalysis activity of AC‐P10 are good. Manganese is the main catalyst of AC‐P(x), and Fe is an accelerant to stimulate the catalytic activity of Mn. The extremely high NO removal activity of AC‐P(x) was due to the synergistic effect of surface functional groups and metals, but the catalysis of metals played a more important role.

CONCLUSION

Pyrolusite is suitable to prepare the AC‐based denitrification catalyst (AC‐P(x)) for SCR NO removal because the Mn and Fe contained in the pyrolusite showed a synergistic effect. © 2017 Society of Chemical Industry
Immune profiles vary seasonally, but are not significantly related to migration distance or natal dispersal, in a migratory songbird
Authors: Kelly Tosha R. , MacGillivray Heather L. , Hobson Keith A. , MacDougall‐Shackleton Scott A. , MacDougall‐Shackleton Elizabeth A.
Published: August 2017

A central tenet of ecoimmunology is that an organism's environment shapes its optimal investment in immunity. For example, the benefits of acquired (relatively pathogen specific) versus innate (nonspecific) immune defenses are thought to vary with the risk of encountering familiar versus unfamiliar pathogens. Because pathogen communities vary geographically, individuals that travel farther during seasonal migration or natal dispersal are predicted to have higher exposure to novel pathogens, and lower exposure to familiar pathogens, potentially favoring investment in innate immunity. During the breeding season, migratory animals’ exposure to familiar pathogens should increase, potentially favoring investment in acquired immunity. We hypothesized that song sparrows Melospiza melodia adjust their constitutive immune profiles in response to risk of encountering novel versus familiar pathogens. We predicted that individuals migrating longer distances (inferred from stable hydrogen isotope analysis of claws) and less philopatric individuals (inferred from microsatellite assignment testing) would rely more heavily on acquired than innate defenses. We also predicted that reliance on acquired defenses would increase throughout the early breeding season. Consistent with trade‐offs between acquired and innate defenses, levels of immunoglobulin Y (acquired) varied negatively with macrophage phagocytosis activity (innate). Levels of acquired relative to innate immunity did not vary significantly with migration distance or philopatry, but increased throughout the early breeding season. Macrophage phagocytosis was not significantly repeatable between years. Song sparrows appear to shift from innate defenses immediately after migration to acquired defenses with increasing time at the breeding grounds. These patterns highlight the plasticity of constitutive immune defenses in migratory animals.
Pseudoinheritance and Chronicity in Social Exclusion: Stressful Life Events in Childhood and Precocious Adulthood Among Trash Pickers in León (Nicaragua)
Authors: Vázquez José Juan
Published: August 2017

This study analyses the stressful life events experienced in childhood and adolescence and the onset of precocious adulthood among individuals who earn their livelihood in the dump (n = 99) in León (Nicaragua). The results show that the trash pickers of León suffered from many stressful life events during their childhood and adolescence, which were extremely serious and occurred from very early ages. Furthermore, these people began to engage in adult activities at a very early age. Both factors may have a significant impact on the chronicity of the trash pickers' social exclusion. Copyright © 2017 John Wiley & Sons, Ltd.
Public Sector Corruption and Trust in the Private Sector
Authors: Gillanders Robert , Neselevska Olga
Published: August 2017

Using Afrobarometer data, we show that experiencing bribery in the course of one's interactions with the public sector lowers one's trust in big private corporations, small businesses and local traders. As trust in market institutions is vital to the efficient functioning of an economy, our findings point to a previously unknown and potentially substantial cost of corruption. This relationship is evident even when we control for perceptions of corruption. Our findings are not driven by corruption lowering interpersonal trust. Having to pay a bribe for household services is the corrupt interaction most strongly associated with the decline in private sector trust. Copyright © 2017 John Wiley & Sons, Ltd.
Characterization of phenolic compounds in green and red oak‐leaf lettuce cultivars by UHPLC‐DAD‐ESI‐QToF/MS using MSE scan mode
Authors: Viacava Gabriela E. , Roura Sara I. , Berrueta Luis A. , Iriondo Carmen , Gallo Blanca , Alonso‐Salces Rosa M.
Published: August 2017

Lettuce (Lactuca sativa) is one of the most popular leafy vegetables in the world and constitutes a major dietary source of phenolic compounds with health‐promoting properties. In particular, the demand for green and red oak‐leaf lettuces has considerably increased in the last years but few data on their polyphenol composition are available. Moreover, the usage of analytical edge technology can provide new structural information and allow the identification of unknown polyphenols. In the present study, the phenolic profiles of green and red oak‐leaf lettuce cultivars were exhaustively characterized by ultrahigh‐performance liquid chromatography (UHPLC) coupled online to diode array detection (DAD), electrospray ionization (ESI), and quadrupole time‐of‐flight mass spectrometry (QToF/MS), using the MSE instrument acquisition mode for recording simultaneously exact masses of precursor and fragment ions. One hundred fifteen phenolic compounds were identified in the acidified hydromethanolic extract of freeze‐dried lettuce leaves. Forty‐eight of these compounds were tentatively identified for the first time in lettuce, and only 20 of them have been previously reported in oak‐leaf lettuce cultivars in literature. Both oak‐leaf lettuce cultivars presented similar phenolic composition, except for apigenin‐glucuronide and dihydroxybenzoic acid, only detected in the green cultivar; and for luteolin‐hydroxymalonylhexoside, an apigenin conjugate with molecular formula C40H54O19 (monoisotopic MW = 838.3259 u), cyanidin‐3‐O‐glucoside, cyanidin‐3‐O‐(3″‐O‐malonyl)glucoside, cyanidin‐3‐O‐(6″‐O‐malonyl)glucoside, and cyanidin‐3‐O‐(6″‐O‐acetyl)glucoside, only found in the red cultivar. The UHPLC‐DAD‐ESI‐QToF/MSE approach demonstrated to be a useful tool for the characterization of phenolic compounds in complex plant matrices.
Circulation type classifications for temperature and precipitation stratification in Italy
Authors: Vallorani Roberto , Bartolini Giorgio , Betti Giulio , Crisci Alfonso , Gozzini Bernardo , Grifoni Daniele , Iannuccilli Maurizio , Messeri Alessandro , Messeri Gianni , Morabito Marco , Maracchi Giampiero
Published: August 2017

During the last few decades, weather circulation type classifications (CTCs) have been widely used to gain insight into processes at the synoptic scale, but also for studying the relationship between atmospheric circulation and surface climate variability. This study aims to evaluate the best performing CTCs based on COST733 software for the stratification of daily ground‐level precipitation and surface air temperature across Italy by means of four statistical metrics. Six classification methods belonging to the four COST733 groups (threshold‐based, PCA‐based, leader algorithms and optimization algorithms) were investigated on 32 and 26 data time series derived from Italian weather stations for daily mean temperature and daily mean precipitation, respectively. CTCs were computed using gridded mean sea level pressure and geopotential height at 500 hPa derived from the NCEP Reanalysis 2 dataset between 1979 and 2015 and tested on three different numbers of classes (8/9, 11/12 and 18 circulation types). Evaluation metrics showed an evident seasonal variability and high‐spatial heterogeneity reflecting the geographical complexity of the Italian territory. The study points out that the best classification, both for temperature and precipitation, is strongly dependent on the classification variable (mean sea level pressure and geopotential height at 500 hPa) showing relevant differences between surface temperature and precipitation. A low number of circulation types (8/9) resulted as the most appropriate grouping for the Italian domain and the Principal Component Transversal and Simulated Annealing were the best performing classification procedures for ground‐level precipitation and temperature stratification, respectively.
Phosphorus availability of sewage sludge‐based fertilizers determined by the diffusive gradients in thin films (DGT) technique
Authors: Vogel Christian , Sekine Ryo , Steckenmesser Daniel , Lombi Enzo , Steffens Diedrich , Adam Christian
Published: August 2017

The plant‐availability of phosphorus (P) in fertilizers and soil can strongly influence the yield of agricultural crops. However, there are no methods to efficiently and satisfactorily analyze the plant‐availability of P in sewage sludge‐based P fertilizers except by undertaking time‐consuming and complex pot or field experiments. We employed the diffusive gradients in thin films (DGT) technique to quantify the plant P availability of various types of P fertilizers with a novel focus on sewage sludge‐based P fertilizers. Mixtures of fertilizer and soil were incubated for 3 weeks at 60% water holding capacity. DGT devices were deployed at the beginning of the incubation and again after 1, 2, and 3 weeks. Two weeks of incubation were sufficient for the formation of plant‐available P in the fertilizer/soil mixtures. In a pot experiment, the DGT technique predicted maize (Zea mays L.) biomass yield and P uptake significantly more accurately than standard chemical extraction tests for P fertilizers (e.g., water, citric acid, and neutral ammonium citrate). Therefore, the DGT technique can be recommended as a reliable and robust method to screen the performance of different types of sewage sludge‐based P fertilizers for maize cultivation minimizing the need for time‐consuming and costly pot or field experiments.
Extra‐virgin olive oil: are consumers provided with the sensory quality they want? A hedonic price model with sensory attributes
Authors: Cavallo Carla , Caracciolo Francesco , Cicia Gianni , Del Giudice Teresa
Published: August 2017

BACKGROUND

Over the years, niche‐differentiation strategies and food policies have pushed quality standards of European extra‐virgin olive oil towards a product that has a sensory profile consisting of fruity, bitter and pungent notes, with such oils having excellent healthy features. However, it is unclear whether typical consumers are ready for a richer and more complex sensory profile than the neutral one historically found on the market. This potential discrepancy is investigated in the present study aiiming to determine whether current demand is able to appreciate this path of quality enhancement. Implicit prices for each and every attribute of extra‐virgin olive oil with a focus on sensory characteristics were investigated using a hedonic price model.

RESULTS

Although confirming the importance of origin and terroir for extra‐virgin olive oil, the results of the present study strongly confirm the discrepancy between what is currently valued on the market and what novel supply trends are trying to achieve in terms of the sensory properties of such products.

CONCLUSION

Increasing consumer awareness about the direct link between the health quality of oils and their sensory profile appears to be necessary to make quality enhancement programs more successful on the market and hence more effective for companies. © 2017 Society of Chemical Industry
Dietary vitamin E dosage and source affects meat quality parameters in light weight lambs
Authors: Leal Leonel N , Beltrán José A , Alonso Verónica , Bello José M , den Hartog Leo A , Hendriks Wouter H , Martín‐Tereso Javier
Published: August 2017

BACKGROUND

Supra‐nutritional vitamin E supplementation is a commonly used approach to delay lipid oxidation and colour deterioration in lamb and beef meat marketed under modified atmosphere packaging. However, these applications lack a precise calibration of dose for the desired effect and, in addition, limited information is available regarding the use of natural vitamin E for this purpose.

RESULTS

Three hundred and sixty Rasa Aragonesa lambs were fed diets supplemented with all‐rac‐α‐tocopheryl acetate (250, 500, 1000 and 2000 mg kg–1 compound feed), RRR‐α‐tocopheryl acetate (125, 250, 500 and 1000 mg kg–1 compound feed) and a basal diet without vitamin E supplementation for 14 days before slaughter at 25.8 ± 1.67 kg body weight. Vitamin E supplementation had no effect (P > 0.05) on average daily weight gain, feed intake and feed efficiency. Display time had larger effects on lipid oxidation, colour stability, myoglobin forms and meat discolouration parameters compared to vitamin E supplementation. However, vitamin E source and dosage significantly extended meat shelf‐life as indicated by lipid oxidation, redness, hue angle, metmyoglobin formation, deoxymyoglobin formation, A580–630 and ISO2.

CONCLUSION

The quantification of these effects demonstrated that the biological activity value of 1.36 used to distinguish both vitamin E sources is not appropriate for meat quality enhancing properties. © 2017 Society of Chemical Industry