bluuebunny/crossref_metadata_2025_split huggingface dataset:
Preparation, surface wetting properties, and protein adsorption resistance of well‐defined amphiphilic fluorinated diblock copolymers
Authors: Zhan Xiaoli , Zhang Guangfa , Zhang Qinghua , Chen Fengqiu 
Published: July 2014

ABSTRACTNovel well‐defined amphiphilic fluorinated diblock copolymers P(PEGMA‐co‐MMA)‐b‐PC6SMA were synthesized successfully by RAFT polymerization and characterized by FTIR, 1HNMR and GPC. For copolymer coatings, static contact angles, θ, with water (θwater ≥ 109.5°) and n‐hexadecane (θhexadecane ≥ 68.9°) pointed to the simultaneous hydrophobic and lipophobic characteristics of the copolymer surfaces. Dynamic contact angle measurements indirectly demonstrated that copolymer films underwent surface reconstruction upon contact with water, which results in a surface with surface coverage of polar PEG units. Moreover, the distinct nanoscale microphase segregation structures were proved by atomic force microscopy (AFM) images. Finally, using bovine serum albumin (BSA–FITC) as the model protein, copolymers exhibited excellent protein adsorption resistance. It is believed that the combination of surface reorganization and nanometer‐scale microphase segregation structure endows the excellent protein resistance for amphiphilic fluorinated copolymers. These results provide deeper insight of the effect of surface reconstruction and microphase segregation on the protein adsorption behaviors, and these amphiphilic fluoropolymers can expect to have potential applications as antifouling coatings in the field of marine and biomedical. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 41167.
Diels–Alder Reaction on Free C68 Fullerene and Endohedral Sc3N@C68 Fullerene Violating the Isolated Pentagon Rule: Importance of Pentagon Adjacency
Authors: Yang Tao , Zhao Xiang , Nagase Shigeru , Akasaka Takeshi 
Published: July 2014

AbstractThe reaction mechanism and regioselectivity of the Diels–Alder reactions of C68 and Sc3N@C68, which violate the isolated pentagon rule, were studied with density functional theory calculations. For C68, the [5,5] bond is the most favored thermodynamically, whereas the cycloaddition on the [5,6] bond has the lowest activation energy. Upon encapsulation of the metallic cluster, the exohedral reactivity of Sc3N@C68 is reduced remarkably owing to charge transfer from the cluster to the fullerene cage. The [5,5] bond becomes the most reactive site thermodynamically and kinetically. The bonds around the pentagon adjacency show the highest chemical reactivity, which demonstrates the importance of pentagon adjacency. Furthermore, the viability of Diels–Alder cycloadditions of several dienes and Sc3N@C68 was examined theoretically. o‐Quinodimethane is predicted to react with Sc3N@C68 easily, which implies the possibility of using Diels–Alder cycloaddition to functionalize Sc3N@C68.
Development of New Two‐Dimensional Small Molecules Based on Benzodifuran for Efficient Organic Solar Cells
Authors: Du Zhengkun , Chen Yanhua , Chen Weichao , Qiao Shanlin , Wen Shuguang , Liu Qian , Zhu Dangqiang , Sun Mingliang , Yang Renqiang 
Published: July 2014

AbstractA new organic small molecule, DCA3TBDF, with a 2D benzo[1,2‐b:4,5‐b′]difuran (BDF) moiety as the central core and octyl cyanoacetate units as the end‐capped blocks, was designed and synthesized for solution‐processed bulk heterojunction solar cells. DCA3TBDF possesses good solubility in common organic solvents such as toluene, CH2Cl2, chlorobenzene, and CHCl3 and good thermal stability with an onset decomposition temperature with 5 % weight‐loss occurring at 361 °C. The DCA3TBDF thin film showed a broad absorption at λ=320–700 nm and high crystallinity. Small‐molecule organic solar cells based on DCA3TBDF and [6,6]‐phenyl‐C61‐butyric acid methyl ester demonstrated promising power conversion efficiency with a high fill factor under the illumination of AM 1.5G (100 mW cm−2).
Single‐dose linezolid pharmacokinetics in critically ill patients with impaired renal function especially chronic hemodialysis patients
Authors: El‐Assal Mona I. , Helmy Sally A. 
Published: July 2014

ABSTRACTBackground and ObjectiveRenal failure patients were treated with linezolid (LZD) for proven or suspected infections by multi‐resistant Gram‐positive cocci. The aim of this study was to determine if dose adjustment of LZD is needed as a function of renal impairment or not, especially that a significant component of LZD is eliminated unchanged in urine.MethodsThe single dose pharmacokinetics of LZD was investigated. Eighteen non‐infected male subjects with various degrees of renal impairment ranged from normal to severe chronic impairment were enrolled, including end‐stage renal disease (ESRD) patients maintained on hemodialysis (HD). LZD was administered as a single oral 600 mg dose, and blood samples were drawn at different times and analysed by a validated HPLC assay method. Plasma profiles were evaluated by non‐compartmental and compartmental approaches.Results and DiscussionA similar rate and extent of LZD absorption and elimination and comparable body exposure was observed in both healthy subjects and acute renal failure patients. The extent of LZD exposure was significantly increased by 3‐fold in ESRD patients in their off‐dialysis day. Furthermore, the t1/2 and MRT values were significantly increased by ~5‐ and 3‐fold, respectively. The Vd/F values of LZD did not change with renal function. A significant decrease in CL/F by ~3‐fold was observed in ESRD patients in their off‐dialysis day however, CL/F was significantly increased by ~4‐fold during HD. Approximately half of the administered LZD dose was removed during the HD session in these selected cohorts of ESRD patients. LZD was generally well tolerated.ConclusionsThe dose of LZD did not need to be adjusted for patients with acute renal dysfunction or ESRD on HD. One of the twice‐daily doses should be administered after the dialysis session because almost half of the LZD dose was substantially removed by HD. During the first three dialysis sessions of the treatment course, to avoid potentially ineffective therapy, a supplemental dose of LZD might be given if necessary or the dose of LZD should be administered 4 h before the beginning of the HD session. This was to keep LZD levels above the MIC for the organism causing the infection being treated. Copyright © 2014 John Wiley & Sons, Ltd.
Essential‐Oil Composition of Daucus carota ssp. major (Pastinocello Carrot) and Nine Different Commercial Varieties of Daucus carota ssp. sativus Fruits
Authors: Flamini Guido , Cosimi Elena , Cioni Pier Luigi , Molfetta Ilaria , Braca Alessandra 
Published: July 2014

AbstractThe chemical composition of the essential oils obtained by hydrodistillation from the pastinocello carrot, Daucus carota ssp. major (Vis.) Arcang. (flowers and achenes), and from nine different commercial varieties of D. carota L. ssp. sativus (achenes) was investigated by GC/MS analyses. Selective breeding over centuries of a naturally occurring subspecies of the wild carrot, D. carota L. ssp. sativus, has produced the common garden vegetable with reduced bitterness, increased sweetness, and minimized woody core. On the other hand, the cultivation of the pastinocello carrot has been abandoned, even if, recently, there has been renewed interest in the development of this species, which risks genetic erosion. The cultivated carrot (D. carota ssp. sativus) and the pastinocello carrot (D. carota ssp. major) were classified as different subspecies of the same species. This close relationship between the two subspecies urged us to compare the chemical composition of their essential oils, to evaluate the differences. The main essential‐oil constituents isolated from the pastinocello fruits were geranyl acetate (34.2%), α‐pinene (12.9%), geraniol (6.9%), myrcene (4.7%), epi‐α‐bisabolol (4.5%), sabinene (3.3%), and limonene (3.0%). The fruit essential oils of the nine commercial varieties of D. carota ssp. sativus were very different from that of pastinocello, as also confirmed by multivariate statistical analyses.
Synthesis of Bio‐Based Methacrylic Acid by Decarboxylation of Itaconic Acid and Citric Acid Catalyzed by Solid Transition‐Metal Catalysts
Authors: Le Nôtre Jérôme , Witte‐van Dijk Susan C. M. , van Haveren Jacco , Scott Elinor L. , Sanders Johan P. M. 
Published: July 2014

AbstractMethacrylic acid, an important monomer for the plastics industry, was obtained in high selectivity (up to 84 %) by the decarboxylation of itaconic acid using heterogeneous catalysts based on Pd, Pt and Ru. The reaction takes place in water at 200–250 °C without any external added pressure, conditions significantly milder than those described previously for the same conversion with better yield and selectivity. A comprehensive study of the reaction parameters has been performed, and the isolation of methacrylic acid was achieved in 50 % yield. The decarboxylation procedure is also applicable to citric acid, a more widely available bio‐based feedstock, and leads to the production of methacrylic acid in one pot in 41 % selectivity. Aconitic acid, the intermediate compound in the pathway from citric acid to itaconic acid was also used successfully as a substrate.
Aerobic Oxidation of Alkylaromatics using a Lipophilic N‐Hydroxyphthalimide: Overcoming the Industrial Limit of Catalyst Solubility
Authors: Petroselli Manuel , Franchi Paola , Lucarini Marco , Punta Carlo , Melone Lucio 
Published: July 2014

Abstract4,4′‐(4,4′‐Isopropylidenediphenoxy)bis(N‐hydroxyphthalimide), which is a new lipophilic analogue of N‐hydroxyphthalimide, can act as an effective catalyst in the aerobic oxidation of alkylaromatics under reduced amounts of polar cosolvent. The catalyst was selected on the basis of an in‐depth study of the influence that substituents on the aromatic ring of N‐hydroxyphthalimide exert on determining the NOH bond dissociation energy (BDE). BDE values for a range of model molecules are calculated by DFT and measured by EPR spectroscopy. The new catalyst can be successfully employed in the aerobic oxidation of cumene, ethylbenzene, and cyclohexylbenzene, affording, in all cases, good conversions and high selectivity for the corresponding hydroperoxide. The effect of solvent, catalyst, and temperature has also been investigated.
Laccase‐Mediator System for Alcohol Oxidation to Carbonyls or Carboxylic Acids: Toward a Sustainable Synthesis of Profens
Authors: Galletti Paola , Pori Matteo , Funiciello Federica , Soldati Roberto , Ballardini Alberto , Giacomini Daria 
Published: July 2014

AbstractBy combining two green and efficient catalysts, such as the commercially available enzyme laccase from Trametes versicolor and the stable free radical 2,2,6,6‐tetramethylpiperidine‐N‐oxyl (TEMPO), the oxidation in water of some primary alcohols to the corresponding carboxylic acids or aldehydes and of selected secondary alcohols to ketones can be accomplished. The range of applicability of bio‐oxidation is widened by applying the optimized protocol to the oxidation of enantiomerically pure 2‐arylpropanols (profenols) into the corresponding 2‐arylpropionic acids (profens), in high yields and with complete retention of configuration.
Selective Conversion of Cellulose in Corncob Residue to Levulinic Acid in an Aluminum Trichloride–Sodium Chloride System
Authors: Li Jianmei , Jiang Zhicheng , Hu Libin , Hu Changwei 
Published: July 2014

AbstractIncreased energy consumption and environmental concerns have driven efforts to produce chemicals from renewable biomass with high selectivity. Here, the selective conversion of cellulose in corncob residue, a process waste from the production of xylose, to levulinic acid was carried out using AlCl3 as catalyst and NaCl as promoter by a hydrothermal method at relatively low temperature. A levulinic acid yield of 46.8 mol % was obtained, and the total selectivity to levulinic acid with formic acid was beyond 90 %. NaCl selectively promoted the dissolution of cellulose from corncob residue, and significantly improved the yield and selectivity to levulinic acid by inhibiting lactic acid formation in the subsequent dehydration process. Owing to the salt effect of NaCl, the obtained levulinic acid could be efficiently extracted to tetrahydrofuran from aqueous solution. The aqueous solution with AlCl3 and NaCl could be recycled 4 times. Because of the limited conversion of lignin, this process allows for the production of levulinic acid with high selectivity directly from corncob residue in a simple separation process.
Efficient Synthesis of Isothiochromene Derivatives by Pd‐Catalyzed Hydrothiolation Reaction
Authors: Feng Jie , Lv Meifang , Lu Guoping , Cai Chun 
Published: July 2014

AbstractAn efficient method for the preparation of isothiochromene derivatives through the palladium‐catalyzed intramolecular hydrothiolation reaction of halides and thiourea is reported. Two carbon–sulfur bonds are formed in this one‐pot palladium‐catalyzed cascade reaction. This new protocol is free from foul‐smelling thiols and operates under mild conditions to give isothiochromene derivatives in excellent yields and with excellent 6‐endo‐dig selectivity.
A Novel Chemoselective Cleavage of (tert‐Butyl)(dimethyl)silyl (TBS) Ethers Catalyzed by Ce(SO4)2⋅4 H2O
Authors: González‐Calderón Davir , González‐González Carlos A. , Fuentes‐Benítez Aydeé , Cuevas‐Yáñez Erick , Corona‐Becerril David , González‐Romero Carlos 
Published: July 2014

Abstract(tert‐Butyl)(dimethyl)silyl (tBuMe2Si; TBS) phenyl/alkyl ethers were efficiently cleaved to the corresponding parent hydroxy compounds in good yields using catalytic amounts of Ce(SO4)2⋅4 H2O by microwave‐assisted or conventional heating in MeOH. Intramolecular and competitive experiments demonstrated the chemoselective deprotection of TBS ethers in the presence of triisopropylsilyl (iPr3Si; TIPS) and (tert‐butyl)(diphenyl)silyl (tBuPh2Si; TBDPS) ethers.
Efficient Total Synthesis of Bioactive Natural Products: A Personal Record
Authors: Zhang Yun , Gong Jianxian , Yang Zhen 
Published: July 2014

AbstractIn this account, we have highlighted our most recent works towards the total synthesis of bioactive natural products, which have resulted in the development of several novel synthetic methods. Inspired and guided by strategies based on diversity‐oriented synthesis, we have successfully applied the novel synthetic methodologies developed in our lab to the total synthesis of a diverse collection of structurally challenging targets. We have also documented the evolution of these synthetic strategies. The total syntheses described in this account have been organized from the perspective of different molecules whilst still alluding to the parallel synthetic strategies involved.
Synthesis of Natural Products Containing Cyclohexane Units Utilizing the Ferrier Carbocyclization Reaction
Authors: Chida Noritaka , Sato Takaaki 
Published: July 2014

AbstractThe Ferrier carbocyclization reaction is one of the most powerful transformations of carbohydrates. This reaction provides enantiomerically pure cyclohexanone derivatives from aldohexoses, and is particularly useful in the chiral pool synthesis of cyclohexane‐containing natural products from carbohydrates. We have investigated the synthesis of natural products utilizing the Ferrier carbocyclization reaction. This account provides a brief overview of the Ferrier carbocyclization and its application to natural product synthesis. The utility and versatility of the Ferrier carbocyclization reaction are showcased with the syntheses of hygromycin A, lycoricidine, actinobolin, galanthamine, and morphine starting from carbohydrates.
ACE for all – a molecular perspective
Authors: Harrison Charlotte , Acharya K. Ravi 
Published: July 2014

AbstractAngiotensin‐I converting enzyme (ACE, EC 3.4.15.1) is a zinc dependent dipeptidyl carboxypeptidase with an essential role in mammalian blood pressure regulation as part of the renin‐angiotensin aldosterone system (RAAS). As such, it has long been targeted in the treatment of hypertension through the use of ACE inhibitors. Although ACE has been studied since the 1950s, only recently have the full range of functions of this enzyme begun to truly be appreciated. ACE homologues have been found in a host of other organisms, and are now known to be conserved in insects. Insect ACE homologues typically share over 30 % amino acid sequence identity with human ACE. Given that insects lack a mammalian type circulatory system, they must have crucial roles in other physiological processes. The first ACE crystal structures were reported during the last decade and have enabled these enzymes to be studied from an entirely different perspective. Here we review many of these key developments and the implications that they have had on our understanding of the diverse functions of these enzymes. Specifically, we consider how structural information is being used in the design of a new generation of ACE inhibitors with increased specificity, and how the structures of ACE homologues are related to their functions. The Anopheles gambiae genome is predicted to code for ten ACE homologues, more than any genome studied so far. We have modelled the active sites of some of these as yet uncharacterised enzymes to try and infer more about their potential roles at the molecular level.
Pecca Fortiter for the Sake of Morality?Making Sense of Wrong in Hegel’s System of Right
Authors: Englert Alexander T. 
Published: July 2014

AbstractThe goal of this paper is to clarify the role ‘wrong’ plays in Hegel’s system of right, as both a form of freedom and the transition to morality. Two approaches will be examined to explore wrong in practical philosophical terms: First, one could take the transition to bedescriptivein nature. The transition describes wrong as a realized fact of the human condition that one inherits from the outset. Second, one could see it asprescriptive. Actual wrongdoing would be essential for the subject’s progression tobecoming moral. Though both are most likely the case, emphasis is given to the latter since it represents the actualization of potential. Furthermore, it will be suggested that wrong plays a similar role as that which alienation does in thePhenomenology of Spirit; both bridge the will as abstract personality with the moral point of view.
Parfit the Perfectionist
Authors: Scruton Roger 
Published: July 2014

AbstractI summarize and criticize Derek Parfit's impressive attempt to reconcile the Kantian and the Consequentialist approaches to moral thinking, and argue that his ‘cognitive non-naturalism’ fails to do justice to the roots of moral sentiment in personal relations. I outline the destructive effect of ‘trolley problems’ on ethical reasoning, and mount a case for seeing moral reasoning as a consequence of ‘reactive’ attitudes, arising from the attempt to reach a rational consensus in the things that we praise and blame.
Children with specific language impairment and their contribution to the study of language development
Authors: LEONARD LAURENCE B. 
Published: July 2014

ABSTRACTChildren with specific language impairment (SLI) are distinguishable from typically developing children primarily in the pace and course of their language development. For this reason, they are appropriate candidates for inclusion in any theory of language acquisition. In this paper, the areas of overlap between children with SLI and those developing in typical fashion are discussed, along with how the joint study of these two populations can enhance our understanding of the language development process. In particular, evidence from children with SLI can provide important information concerning the role of language typology in language development, the optimal ages for acquiring particular linguistic details, the robustness of the bilingual advantage for children, the role of input in children's acquisition of grammatical details, the unintended influence of processing demands during language assessment, the contributions of treatment designs to the study of typically developing children, and the study of individual differences in language development.
Empirical support for problem–solution coevolution in a parametric design environment
Authors: Yu Rongrong , Gu Ning , Ostwald Michael , Gero John S. 
Published: July 2014

AbstractThis paper describes the results of a protocol study exploring problem–solution coevolution in a parametric design environment (PDE). The study involved eight participants who completed a defined architectural design task using Rhino and Grasshopper software: a typical PDE. The method of protocol analysis was employed to study the cognitive behaviors that occurred while these designers were working in the PDE. By analyzing the way in which the designers shifted between “problem” and “solution” spaces in the PDE, characteristics of the coevolutionary design process are identified and discussed. Results of this research include two potentially significant observations. First, the coevolution process occurs frequently within the design knowledge level (i.e., when using Rhino) and within the rule algorithm level (i.e., when using Grasshopper) of the parametric design process. Second, the designers’ coevolution process was focused on the design knowledge level at the beginning of the design session, while they focused more on the rule algorithm level toward the end of the design session. These results support an improved understanding of the design process that occurs in PDEs.
Expansion of the fusion stalk and its implication for biological membrane fusion
Authors: Risselada Herre Jelger , Bubnis Gregory , Grubmüller Helmut 
Published: July 2014

Significance
We focus on computing lipidic fusion pathway energetics and interpret them in a biological context. We illustrate that the progression of fast synaptic fusion may not rely on the point-like forces that are being transmitted to the membrane via the transmembrane domains of SNARE molecules. Our work bridges the many present gaps between diverse but related experiments and their interpretation, thus providing a coherent and integrative picture.
Acuity-independent effects of visual deprivation on human visual cortex
Authors: Hou Chuan , Pettet Mark W. , Norcia Anthony M. 
Published: July 2014

Significance
Deviation of the direction of two eyes (strabismus) or chronic optical blur (anisometropia) separately and together can disrupt the development of visual cortex. To shed new light on how these two forms of visual deprivation affect cortical development, we used event-related potentials coupled with a stimulation paradigm to study the temporal evolution of visual responses in patients who had experienced either strabismus or anisometropia early in life. Our results indicate that strabismus generates significant abnormalities at both early and later stages of cortical processing and, importantly, that these abnormalities are independent of visual-acuity deficits. The nonamblyopic eyes of anisometropic amblyopes, by contrast, are normal, suggesting that these two forms of visual deprivation are differentiated very early in visual cortex.