bluuebunny/crossref_metadata_2025_split huggingface dataset:
Allylic oxidation of methyl 10‐undecenoate and nucleophilic additions to methyl 9‐oxo‐10‐undecenoate
Authors: Hinkamp Ludger , Schäfer Hans J. 
Published: December 2014

AbstractMethyl 10‐undecenoate (2b) has been oxidized with tert‐butyl hydroperoxide/selenium dioxide and potassium dichromate to 53% of methyl 9‐oxo‐10‐undecenoate (4). Based on the conversion of 2b, the yield of 4 is 81%. Residual selenium in ester 5 was determined to be less than 1 ppm. The electrophilic double bond in enone 4 reacts in good to excellent yield with a variety of nucleophiles. With dimethyl malonate, acetylacetone, and methyl acetoacetate Michael–adducts at C‐11 of enone 4 were obtained in 88–99% yield. Corresponding additions were achieved with nitroethane, 1‐ and 2‐nitropropane in 78–89% yield. In a Nef–reaction some nitroalkyl adducts were converted to methyl esters of 9,12‐dioxofatty acids in 99% yield. In methanol/sodium methoxide the ester methyl 11‐methoxy‐9‐oxoundecanoate was obtained in 86% yield from enone 4. In a three step reaction with ammonium chloride/sodium cyanide, hydrochloric acid/acetic acid, and methanol/2,2‐dimethoxypropane the ester 4 yielded 63% of dimethyl 4‐oxo‐dodecanedioate. With the cyanide ion the electrophilic carbon atom in aldehydes can be converted into a nucleophile (Stetter–reaction). Catalysed by sodium cyanide in DMF aromatic and heteroaromatic aldehydes RCHO with R = phenyl, 2‐thienyl, 2‐furyl and 3‐pyridyl were added to enone 4 to afford methyl 12‐aryl‐ and methyl 12‐heteroaryl‐9,12‐dioxododecanoates in 54–73% yield.Practical applications: The prepared oleochemicals are useful as precursors for pharmaceuticals and as monomers for polyesters and polyamides. They also may be applied to synthesize fatty acid conjugates by providing suitable connectors for biological active compounds and to attach groups with suitable physical properties for materials.For enone 4 prepared from methyl 10‐undecenoate, thirteen Michael additions with 1,3‐dicarbonyl and nitro alkyl compounds, hydrocyanic acid and acyl anions are reported.
A Metal‐Catalyzed Tandem 1,4‐Benzodiazepine Synthesis Based on Two Hydrogen‐Transfer Reactions
Authors: Jumde Varsha R. , Cini Elena , Porcheddu Andrea , Taddei Maurizio 
Published: December 2014

AbstractStarting from 2‐aminobenzyl alcohols and 1,2‐amino alcohols, 2,3,4,5‐tetrahydro‐1H‐1,4‐benzodiazepines (TH‐BDZ) can be prepared through a one‐pot ruthenium‐catalyzed reaction encompassing two consecutive borrowing hydrogen cycles. First, benzyl alcohol oxidation, condensation with the amino alcohol, and imine reduction occurs. This is followed by oxidation of the other alcohol functionality and reductive cyclocondensation to give the TH‐BDZ derivatives. A single catalyst does the entire job, with two molecules of water being the only waste product. Many new substituted 2,3,4,5‐tetrahydro‐1H‐1,4‐benzodiazepines have been prepared to demonstrate the versatility of this method, which can be used for the preparation of privileged scaffolds for drug discovery.
Multigram Synthesis of Fluoroalkyl‐Substituted Pyrazole‐4‐carboxylic Acids
Authors: Iminov Rustam T. , Mashkov Alexander V. , Vyzir Ivan I. , Chalyk Bohdan A. , Tverdokhlebov Anton V. , Mykhailiuk Pavel K. , Babichenko Ludmila N. , Tolmachev Andrey A. , Volovenko Yulian M. , Biitseva Angelina , Shishkin Oleg V. , Shishkina Svetlana V. 
Published: December 2014

AbstractAcylation of tert‐butyl 3‐(methylamino)but‐2‐enoate with fluorinated acetic acid anhydrides occurred at the enamine carbon atom. The reaction of the resulting tert‐butyl 3‐(methylamino)‐2‐(RFCO)but‐2‐enoates with alkyl hydrazines resulted in mixtures of isomeric pyrazoles that were easily separated by column chromatography. The target fluorinated pyrazole‐4‐carboxylic acids were obtained on a multigram scale.
From Chrysene to Double [5]Helicenes
Authors: Bock Harald , Huet Stephanie , Dechambenoit Pierre , Hillard Elizabeth A. , Durola Fabien 
Published: December 2014

AbstractGlyoxylic functionalization of chrysene by Friedel–Crafts acylation with ethyl chloroglyoxylate or by bromination followed by substituent exchange enables the formation of bis[5]helicene‐tetracarboxylates and tetracarboxdiimides through Perkin reactions and palladium‐catalyzed cyclizations. Tetrasubstituted bishelicenic dichrysenoanthracenes and dinaphthochrysenes are thus obtained from chrysene in four to six steps. In the cyclization to dinaphthochrysenes, a rearrangement of the conjugated carbon skeleton is identified as side reaction. In solution, the diimides form mixtures of M,P‐ and M,M/P,P‐diastereomers, which equilibrate at room temperature when the helices are distant but equilibrate only upon heating when the helices are close and acting in concert. The nonplanar arene geometry allows close π‐contacts in two dimensions between neighboring molecules in the crystal.
Divergent Phosphine‐Catalyzed [2+4] or [3+2] Cycloaddition Reactions of γ‐Substituted Allenoates with Oxadienes
Authors: Li Erqing , Chang Meijia , Liang Ling , Huang You 
Published: December 2014

AbstractA strategy was developed to construct dihydropyran and multifunctional cyclopentene derivatives from the same starting materials by using different phosphine catalysts. By exploiting the different nucleophilicities of the phosphine catalysts, the γ‐substituted allenoates selectively acted as C3 or C2 synthons. Under the catalysis of different organophosphine catalysts, the domino reaction proceeded smoothly with broad substrate tolerance and excellent total yields. The results suggest that the ethyl group of the γ‐substituted allenoates played a key role in the domino reaction.
Palladium‐Catalyzed α‐Selective Alkenylation of Imidazo[1,2‐a]pyridines through Aerobic Cross‐Dehydrogenative Coupling Reaction
Authors: Ghosh Monoranjan , Naskar Aswini , Mitra Shubhanjan , Hajra Alakananda 
Published: December 2014

AbstractThe palladium‐catalyzed highly regioselective vinylation of imidazopyridines through a cross‐dehydrogenative coupling reaction was developed. The reaction proceeds with the aid of molecular oxygen as the sole oxidant. A series of branched α‐vinylated products were obtained with high efficiency.
Chemo‐ and Stereoselective Reduction of β‐Keto‐α‐oximino Nitriles by Using Baker's Yeast
Authors: Mo Kilwoong , Kang Soon Bang , Kim Youseung , Lee Yong Sup , Lee Jae Wook , Keum Gyochang 
Published: December 2014

AbstractThe baker's yeast mediated reduction of β‐keto‐α‐oximino nitriles 3 at 20 °C gave β‐hydroxy‐α‐oximino nitriles 4 in high yields with high enantiomeric purity [enantiomeric excess (ee) values >99 %]. At room temperature, the same reaction afforded the product in a slightly lower yield. The β‐hydroxy‐α‐oximino nitriles 4 were obtained as single stereoisomers according to chiral GC–MS analyses and the 1H and 19F NMR spectra of the corresponding Mosher esters. The absolute stereochemistry of alcohol 4a was determined by hydrolysis of its oximino nitrile group followed by conversion into its corresponding α‐hydroxy ester. The β‐hydroxy‐α‐oximino nitrile products were further submitted to oxime‐ and nitrile‐selective transformations. This chemo‐ and stereoselective reduction can be used to generate important chiral building blocks.
Rhodium(I)‐Catalyzed Cycloisomerization of Allene–Allenylcyclopropanes
Authors: Kawamura Takamasa , Kawaguchi Yasuaki , Sugikubo Katsuya , Inagaki Fuyuhiko , Mukai Chisato 
Published: December 2014

AbstractThe RhI‐catalyzed intramolecular [5+2–2]‐type cycloisomerization of allene–allenylcyclopropanes was developed. In this reaction, ethylene was liberated from the cyclopropane ring to afford the 1,5,6,7‐tetrahydroazulene skeletons.
Needs: Defining What You Are Assessing
Authors: Watkins Ryan , Kavale Jolanta 
Published: December 2014

AbstractBy definition your needs assessment should assess needs, but how do you define them? Further, how do you operationalize that definition to measure needs? Do your partners and stakeholders also hold the same conceptual, and operational, definitions? Is there agreement that the project is only going to assess needs and not wants, assets, capacity, or solutions? Or are you really expected to assess all five? Each of these is an important consideration that can substantially influence the success of any needs assessment. In this chapter, the authors examine how definitions and use of the word need influence the design and implementation of an assessment, suggesting that the definition can shape the results of what is found.
Needs Assessment: The Perspective From the Public Sector
Authors: Engle Molly , Altschuld James W. 
Published: December 2014

AbstractWhile examining needs is common in many public‐sector agencies, questions arise about how it has been carried out and if a focus on deficits (or gaps) is too narrow when not accompanied by the assessment of assets. The authors operate in this chapter as actors in a play. The first author offers a short personal perspective about her long experience in the public sector, with emphasis on Extension and the nature of needs assessment within it. In that discussion are two illuminative historical examples with clear relevance to what we might do today. They demonstrate that linking asset‐thinking to such efforts might be a good thing when embarking upon improvement of programs for the public. The second author enters in by amplifying the examination of assets and how they might be linked to the thinking of public‐sector assessors. The authors conclude by recommending that such an expansion of the toolkit of needs assessors would be useful.
International Perspectives: Similarities and Differences Around the Globe
Authors: Meiers Maurya West , Watkins Ryan , Song Kristin Marsh 
Published: December 2014

AbstractNeeds are not uniquely American. From Johannesburg and Helsinki to Cairo and Santiago, they are assessed around the world in a variety of contexts and conditions. Needs assessments often cross borders and cultural boundaries, attempting to systematically assist communities, organizations, and people in making better informed decisions. This complexity can improve the results of an assessment, while at the same time presenting the assessor and the methods used with many practical challenges. In response, the focus of this chapter has to do with successfully conducting needs assessments in diverse international contexts. Offering practical tips, the foundation of the chapter provides real‐world guidance for handling many of the obstacles faced in needs assessments.
Volatile constituents of vetiver: a review
Authors: Belhassen Emilie , Filippi Jean‐Jacques , Brévard Hugues , Joulain Daniel , Baldovini Nicolas 
Published: December 2014

ABSTRACTA comprehensive and critical compilation of the volatile constituents of vetiver root (Chrysopogon zizanioides L.) is presented, including those present in its essential oil. This extremely complex material has stimulated analytical research for many decades in the hope of unravelling the secrets of its composition. Up to now, more than 300 molecules have been reported, mostly sesquiterpenoids possessing a large variety of skeletons, together with their norterpenic counterparts. This review attempts to clarify some of the discrepancies related to the characterization of these constituents, which were often due to the misuses of analytical methods without enough critical consideration of the literature. The identification of the main odour impact components of vetiver is also discussed, because much contradictory information appears in the literature on this subject. Copyright © 2014 John Wiley & Sons, Ltd.
Computer‐aided molecular pathology interpretation in exploring prospective markers for oral submucous fibrosis progression
Authors: Anura Anji , Conjeti Sailesh , Das Raunak Kumar , Pal Mousumi , Paul Ranjan Rashmi , Bag Swarnendu , Ray Ajoy Kumar , Chatterjee Jyotirmoy 
Published: December 2014

AbstractBackgroundEvaluation of molecular pathology markers using a computer‐aided quantitative assessment framework would help to assess the altered states of cellular proliferation, hypoxia, and neoangiogenesis in oral submucous fibrosis and could improve diagnostic interpretation in gauging its malignant potentiality.MethodsImmunohistochemical (IHC) expression of c‐Myc, hypoxia‐inducible factor‐1‐alpha (HIF‐1α), vascular endothelial growth factor (VEGF), VEGFRII, and CD105 were evaluated in 58 biopsies of oral submucous fibrosis using computer‐aided quantification. After digital stain separation of original chromogenic IHC images, quantification of the diaminobenzidine (DAB) reaction pattern was performed based on intensity and extent of cytoplasmic, nuclear, and stromal expression.ResultsAssessment of molecular expression proposed that c‐Myc and HIF‐1α may be used as strong screening markers, VEGF for risk‐stratification and VEGFRII and CD105 for prognosis of precancer into oral cancer.ConclusionOur analysis indicated that the proposed method can help in establishing IHC as an effective quantitative immunoassay for molecular pathology and alleviate diagnostic ambiguities in the clinical decision process. © 2015 Wiley Periodicals, Inc. Head Neck 38: 653–669, 2016
MicroRNA expression as predictor of local recurrence risk in oral squamous cell carcinoma
Authors: Ganci Federica , Sacconi Andrea , Manciocco Valentina , Sperduti Isabella , Battaglia Paolo , Covello Renato , Muti Paola , Strano Sabrina , Spriano Giuseppe , Fontemaggi Giulia , Blandino Giovanni 
Published: December 2014

ABSTRACTBackgroundOral squamous cell carcinoma (OSCC) is the sixth most common cancer worldwide with a high rate of recurrence. MicroRNAs (miRNAs) are gene regulators playing an important role in oral carcinogenesis. The purpose of this study was for us to identify and functionally characterize miRNAs that predict recurrence in OSCC.MethodsWe collected 92 OSCC with their normal tissue counterparts and we performed miRNAs expression profiling on 74 OSCC and 38 normal tissues. The association between the expression of miRNAs and clinical outcome was evaluated in the follow‐up of 69 patients.ResultsFour of the miRNAs deregulated between OSCC and normal tissues are prognostic for recurrence either when considered individually or as a group. Depletion of the expression of prognostic miRNAs inhibit the proliferation of OSCC cellsConclusionMiRNAs are differentially expressed in OSCC versus normal samples. The expression of 4 prognostic miRNA signatures is able to predict recurrence risk independently from other clinical factors in OSCC. © 2015 Wiley Periodicals, Inc. Head Neck 38: E189–E197, 2016
Multicultural Personality and Posttraumatic Stress in U.S. Service Members
Authors: Herrera Catherine J. , Owens Gina P. 
Published: December 2014

ObjectiveModern military missions place numerous demands on service members, including tactical, personal, and cultural challenges. The purpose of this study was to explore how domains of multicultural personality (cultural empathy, open‐mindedness, social initiative, emotional stability, and flexibility) and combat exposure relate to posttraumatic stress disorder (PTSD) in service members.MethodParticipants (N = 163) completed the Multicultural Personality Questionnaire, Combat Exposure Scale, and PTSD Checklist–Military as part of an online survey. The majority of participants were Caucasian (87%), mean age was 33 years, and all were deployed at least once to Iraq or AfghanistanResultsRegression results indicated that higher levels of combat exposure and open‐mindedness and lower levels of flexibility and emotional stability were significant predictors of higher PTSD severity. The interactions between combat exposure and flexibility and combat exposure and openness were also significant.ConclusionHigher levels of flexibility and emotional stability seem particularly important in their association with lower PTSD severity for service members.
Coping Skill as a Moderator Between Negative Life Events and Suicide Among Young People in Rural China
Authors: Sun Long , Zhang Jie 
Published: December 2014

ObjectiveIn the present study, we aim to test whether the approach or the avoidance coping skill can be a moderator between negative life events and suicide, and to test the deficient coping strain in the strain theory.MethodThis sample comprised 392 suicide cases and 416 community living controls, aged 15–34 years, from 16 rural counties in China. An established psychological autopsy method and a case–control design were used in this study. The 48‐item Coping Response Inventory evaluated the degree of coping skills of the people who died by suicide.ResultsResults indicated that the avoidance coping skill, but not the approach coping skill, can moderate between negative life events and suicide.ConclusionThe low level of the avoidance coping skill may represent a promising variable for screening for suicide risk in rural China.
Identity Disturbance and Problems With Emotion Regulation Are Related Constructs Across Diagnoses
Authors: Neacsiu Andrada D. , Herr Nathaniel R. , Fang Caitlin M. , Rodriguez Marcus A. , Rosenthal M. Zachary 
Published: December 2014

ObjectiveThis study examined the relation between identity disturbance and emotion dysregulation in a cross‐diagnostic sample. We assessed whether these constructs are related and relevant beyond borderline personality disorder (BPD).MethodWe recruited 127 participants who completed measures assessing identity disturbance, emotion dysregulation, anxiety, and depression. The sample included primarily depressed adults meeting criteria for multiple diagnoses as well as psychiatrically healthy participants.ResultsIdentity disturbance was significantly higher among psychiatric participants with and without BPD compared to healthy controls. Emotion dysregulation was a significant predictor of identity disturbance, even when controlling for BPD diagnosis, depression, and anxiety. In particular, clarity in emotional situations and problems using emotion regulation strategies were most closely related to identity disturbance.ConclusionThe results of this study suggest that future research should examine identity disturbance and its relation with emotion regulation transdiagnostically.
Do Child Abuse and Maternal Care Interact to Predict Military Sexual Trauma?
Authors: Wilson Laura C. , Kimbrel Nathan A. , Meyer Eric C. , Young Keith A. , Morissette Sandra B. 
Published: December 2014

ObjectiveThe present research tested the hypothesis that maternal care moderates the relationship between childhood sexual abuse and subsequent military sexual trauma (MST).MethodMeasures of childhood sexual abuse, maternal care, and MST were administered to 197 Iraq and Afghanistan war veterans.ResultsAfter accounting for gender, age, and the main effects of maternal care and childhood sexual abuse, the maternal care x childhood sexual abuse interaction was a significant predictor of MST (odds ratio = .28, β = −1.26, 95% confidence intervals of .10, .80). As hypothesized, rates of MST were higher among veterans who reported childhood sexual abuse and low levels of maternal care (43%) compared with veterans who reported childhood sexual abuse and high levels of maternal care (11%).ConclusionThese findings suggest that high levels of maternal care may act as a protective factor against future revictimization among military service members. These findings have the potential to inform both prevention and intervention efforts.
Effects of high heel wear and increased weight on the knee during walking
Authors: Titchenal Matthew R , Asay Jessica L , Favre Julien , Andriacchi Thomas P , Chu Constance R 
Published: December 2014

ABSTRACTKnee osteoarthritis (OA), a leading cause of disability, is more prevalent in women than men. Wearing high heeled shoes has been implicated as a potential contributing factor for the higher lifetime risk of osteoarthritis in women. This study tests the hypotheses that changes to knee kinematics and kinetics observed during high heeled walking increase in magnitude with increasing heel height and are accentuated by a 20% increase in weight. Fourteen healthy females were tested using marker‐based gait analysis in combinations of footwear (flat athletic shoe, 3.8 cm and 8.3 cm heeled shoes) and weight (with and without 20% bodyweight vest). At preferred walking speed, knee flexion angle at heel‐strike and midstance increased with increasing heel height and weight. Maximum knee extension moment during loading response decreased with added weight; maximum knee extension moment during terminal stance decreased with heel height; maximum adduction moments increased with heel height. Many of the changes observed with increasing heel height and weight were similar to those seen with aging and OA progression. This suggests that high heel use, especially in combination with additional weight, may contribute to increased OA risk in women. © 2014 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res 33:???–???, 2015.
A diatom record of mid‐ to late Holocene palaeoenvironmental changes in the southern Okinawa Trough
Authors: LI DONGLING , JIANG HUI , KNUDSEN KAREN LUISE , BJÖRCK SVANTE , OLSEN JESPER , ZHAO MEIXUN , LI TIEGANG , LI JIALIN 
Published: December 2014

ABSTRACTPalaeoceanographic changes over the last 6800 years are documented in a diatom record from core MD05–2908 from the southern Okinawa Trough. Changes in diatom components are used to reflect variations in the strength of the Kuroshio Current and the influence of coastal waters, and these changes are compared with records of the East Asian summer monsoon, which exerts an important influence on regional climate and oceanography. A decreasing trend in the contribution of coastal diatoms during the last 6800 years is related to the weakening of the East Asian summer monsoon during the Holocene in response to diminishing insolation and a southward shift in the intertropical convergence zone. Relatively high abundances of the Kuroshio Current indicator species during the intervals 2600–2200 and 4800–3600 cal a BP, and lower abundances during the intervals 3200–2800 and 2200–1300 cal a BP, imply that there is no consistent weakening of the Kuroshio Current during the interval 4500–3000 cal a BP − the Pulleniatina Minimum Event, which is a widespread feature in the East China Sea and the South China Sea. A major reduction in coastal diatoms at 3200 cal a BP and a slight decrease in the Kuroshio Current indicator species during the interval 3200–2800 cal a BP indicate that a palaeoceanographic shift occurred in the southern Okinawa Trough, which coincided with a Northern Hemisphere climatic cooling, denoted the Neoglaciation in Europe. In addition, changes in the freshwater species component of the record are suggested mainly to result from variations in flood frequency in north‐eastern Taiwan caused by typhoons. A dramatic increase in the frequency of flood events during the last millennium may have been caused by relatively strong El Niño‐Southern Oscillation activity, compared with the more stable period between 6800 and 1000 cal a BP, which experienced a low frequency of flood events.