bluuebunny/crossref_metadata_2025 huggingface dataset:
Colorants for Foods, Drugs, and Cosmetics
Authors: Marmion Daniel ,   Updated by Staff
Published: July 2012

Colorants have been added to foods, drugs, and cosmetics for centuries. Natural sources were used as dyes until the discovery of the first synthetic organic dyestuff by Perkin in 1856. A host of new and different colorants became available. The use of these new dyes in food, drugs, and cosmetics increased rapidly. The proliferation of color additives was soon recognized as a public health concern and it was soon made clear that some sort of government control was necessary.

In 1938 the Federal Food, and Drug, and Cosmetic Act was instituted and several new and important practices were enacted. Among other restrictions the law stated that colorants that could be used were limited, certification became mandatory, and governmental control was extended to the coloring of drugs and cosmetics. Most colorants used today have specifications that must be met before sold. Typical specifications are given. Colorants can be divided into two groups: those listed for use and those provisionally listed. Azo colors comprise the largest group of certified colorants. Colorants are exempt from certification when it is believed that certification is not necessary to protect the public health. In general, exempt colorants have less coloring power than the certified colors and have to be used at higher concentrations. Certified and exempt colors for food, drugs, and cosmetics are listed. Opportunities for natural colorants are discussed.
Emulsions
Authors: Kostansek Edward ,   Updated by Staff
Published: July 2012

An emulsion is a dispersion of one liquid in another, immiscible liquids usually in the presence of stabilizer molecules are called emulsifiers. Emulsions may be either oil droplets dispersed in water or water droplets dispersed in oil wherein the droplet diameters are in the 0.05–100 µm range. Emulsifiers may be anionic, cationic, nonionic, or combinations of ionic and nonionic. The droplets are usually formed by high shear mechanical processes and stabilized by electrostatic and/or steric barriers around the droplets provided by the emulsifiers. Emulsions often require complex mixtures of emulsifiers and are not thermodynamically stable, therefore preparing them is still somewhat of an art. When an emulsion is destabilized, it is said to break into the separate liquid layers. A less severe form of instability is called creaming and involves the droplets rising to the top of the sample where they can be redispersed with proper mixing. Emulsions can be explained using theories of colloid science. Emulsions are found in a wide variety of applications and include food, cosmetics, household products, pharmaceuticals, agricultural applications, road surfacing, latexes, and oil recovery.
Foams
Authors: Saint‐James Arnaud , Durian Douglas J. , Weitz David A. ,   Updated by Staff
Published: July 2012

Foam is a nonequilibrium dispersion of gas bubbles in a relatively smaller volume of liquid containing surface‐active molecules. Foams that are relatively stable can be thought of as a form of condensed matter both solid‐like in being able to resist shear elasticity, and liquid‐like in being able to flow and deform into arbitrary shapes. The extent to which macroscopic stability and rheology of liquid‐based foams can be understood in terms of the underlying structure and dynamics of the constituent gas bubbles and liquid films, and their ultimate origin in terms of the physical chemistry of surface‐active molecules preferentially absorbed at the gas‐liquid interfaces are reviewed. Existing measurement techniques and applications such as use in firefighting, oil recovery, cosmetics, food, separations, and detergents are discussed.
Hydrogels
Authors: Cai Wensheng , Gupta Ram B. ,   Updated by Staff
Published: July 2012

Hydrogels are hydrophilic polymer networks that are able to swell and retain large amounts of water and maintain three‐dimensional swollen structures. These hydrogels do not dissolve in water. Common monomers and polymerization methods are discussed as well as synthesis and mechanism of biodegradable hydrogels. Responsive hydrogels can reversibly change volume in response to slight changes in the properties of the medium including pH, temperature, electric field, ionic strength, salt type, solvent, external stress or light. Microgels are cross‐linked microparticles that are swollen by a good solvent and have globular structure. Due to their compact structure the intrinsic viscosities of these microgels are much lower than those of the corresponding liner or branched polymers. Hydrogels are used in molecular separation based on size exclusion, protein isolation by conjugating, in drug delivery, as artificial organs, in tissue engineering, in wound dressings, as fire protection, as superabsorbent material in diapers, water sealing, agricultural applications, and in cosmetics products. For cosmetics, hydrogels provide emulsion stability and conditioning, and therapeutics agents can be added to the hydrogel.
Citrus Oils and Essences
Authors: Shahidi Fereidoon , Zhong Ying
Published: July 2012

Citrus fruits are among the most popular fruits and have a long history of production and use. However, within the past century, industrial technologies have began to develop in order to convert citrus fruits into commercial products. Citrus has proven to be a very good option for oil and essence production. Citrus peel oils are of a very complex composition and are contained in oval, balloon‐shaped oil sacs, or vesicles locate in the outer rind, or flavedo, of the fruit The oil is usually extracted by mechanical separation or hydrodistillation.Citrus seeds are regarded as a new source of oil. The seed oil is recovered from the seeds by crushing and solvent extraction. Citrus essences are distilled aqueous solutions of more volatile components from the corresponding citrus juices.Citrus peel oils are used widely in beverages, cosmetics, pharmaceuticals, and the perfumery industry. Seed oils are used in cooking and the treatment of leather and textiles. Quality and freshness are the major considerations pertaining to their value and applications. Most of the qualitative changes in citrus peel oil occur during storage.Storage changes and chemical composition of the citrus oils are described. Despite increasing application of these oils, certain challenges related to potential health‐damaging properties and contamination exist. These health and safety factors are discussed.
Lipids, Pharmaceutical and Cosmetic Use
Authors: Hernandez Ernesto
Published: July 2012

Lipid nutritional supplements have been in use before the term nutraceutical was coined. Products such as fish oils, shark cartilege, shark liver oil, and vitamins have been in the market since the beginning of the twentieth century. Some of the health claims of these products lacked strict scientific documentation in the past, and their curative properties were mostly anecdotal. However there is a better understanding of the biological properties of lipids and their application has extended to pharmaceuticals and cosmetics fields, such as disease prevention and treatment, excipients and coadjuvants, trans‐dermal carriers and skin emolliency agents. This has led to the development of bioactive cosmetic and pharmaceutical products whose name is coined as cosmeceutical.
Flirting With Disaster: Short‐Term Mating Orientation and Hostile Sexism Predict Different Types of Sexual Harassment
Authors: Diehl Charlotte , Rees Jonas , Bohner Gerd
Published: July 2012

We combine evolutionary and sociocultural accounts of sexual harassment, proposing that sexuality‐related and hostility‐related motives lead to different types of harassment. Specifically, men's short‐term mating orientation (STMO) was hypothesized to predict only unwanted sexual attention but not gender harassment, whereas men's hostile sexism (HS) was hypothesized to predict both unwanted sexual attention and gender harassment. As part of an alleged computer‐chat task, 100 male students could send sexualized personal remarks (representing unwanted sexual attention), sexist jokes (representing gender harassment), or nonharassing material to an attractive female target. Independently, participants’STMO,HS, and sexual harassment myth acceptance (SHMA) were assessed. Correlational and path analyses revealed thatSTMOspecifically predicted unwanted sexual attention, whereasHSpredicted both unwanted sexual attention and gender harassment. Furthermore,SHMAfully mediated the effect ofHSon gender harassment, but did not mediate effects ofSTMOorHSon unwanted sexual attention. Results are discussed in relation to motivational explanations for sexual harassment and antiharassment interventions. Aggr. Behav. 38:521‐531, 2012. © 2012 Wiley Periodicals, Inc.
Binary and Ternary Atomic Layers Built from Carbon, Boron, and Nitrogen
Authors: Song Li , Liu Zheng , Reddy Arava Leela Mohana , Narayanan Narayanan Tharangattu , Taha‐Tijerina Jaime , Peng Juan , Gao Guanhui , Lou Jun , Vajtai Robert , Ajayan Pulickel M.
Published: July 2012

Two‐dimensional (2D) atomic layers derived from bulk layered materials are very interesting from both scientific and application viewpoints, as evidenced from the story of graphene. Atomic layers of several such materials such as hexagonal boron nitride (h‐BN) and dichalcogenides are examples that complement graphene. The observed unconventional properties of graphene has triggered interest in doping the hexagonal honeycomb lattice of graphene with atoms such as boron (B) and nitrogen (N) to obtain new layered structures. Individual atomic layers containing B, C, and N of various compositions conform to several stable phases in the three‐component phase diagram of B–C–N. Additionally, stacking layers built from C and BN allows for the engineering of new van‐der‐Waals stacked materials with novel properties. In this paper, the synthesis, characterization, and properties of atomically thin layers, containing B, C, and N, as well as vertically assembled graphene/h‐BN stacks are reviewed. The electrical, mechanical, and optical properties of graphene, h‐BN, and their hybrid structure are also discussed along with the applications of such materials.
Reverse osmosis performance of organosilica membranes and comparison with the pervaporation and gas permeation properties
Authors: Xu Rong , Wang Jinhui , Kanezashi Masakoto , Yoshioka Tomohisa , Tsuru Toshinori
Published: July 2012

Hybrid organosilica membranes were successfully prepared using bis(triethoxysilyl)ethane (BTESE) and applied to reverse osmosis (RO) desalination. The organosilica membrane calcined at 300°C almost completely rejected salts and neutral solutes with low‐molecular‐weight. Increasing the operating pressure led to an increase in water flux and salt rejection, while the flux and rejection decreased as salt concentration increased. The water permeation mechanism differed from the viscous flow mechanism. Observed activation energies for permeation were larger for membranes with a smaller pore size, and were considerably larger than the activation energy for water viscosity. The organosilica membranes exhibited exceptional hydrothermal stability in temperature cycles up to 90°C. The applicability of the generalized solution‐diffusion (SD) model to RO and pervaporation (PV) desalination processes were examined, and the quantitative differences in water permeance were accurately predicted by the application of generalized transport equations. © 2012 American Institute of Chemical Engineers AIChE J, 59: 1298–1307, 2013
Tailoring of surface oxygen‐containing functional groups and their effect on adsorptive denitrogenation of liquid hydrocarbons over activated carbon
Authors: Li Na , Zhu Jian , Ma Xiaoliang , Zha Qingfang , Song Chunshan
Published: July 2012

The objective of this study is to get a fundamental understanding of role of surface oxygen‐contained functional groups (OCFG) in adsorptive denitrogenation (ADN) of liquid hydrocarbons over activated carbon, and thus to improve the ADN performance of activated carbon through modification of surface chemistry of activated carbon. A set of activated carbon samples with different amount and distribution of OCFG was prepared by oxidative modification and thermal treatment of a commercial activated carbon. The prepared activated carbons were characterized by the temperature‐programmed desorption coupled with mass spectrometry for the concentration of various OCFG, and evaluated in a fixed‐bed adsorption system using a model fuel containing aniline, indole, quinoline, carbazole, and ethyl‐carbazole. The results indicate that OCFG, especially the strong carboxyls, weak carboxyls and anhydrides, play a crucial role in determining the adsorptive performance of activated carbon for selective removal of nitrogen compounds from liquid hydrocarbons. The adsorption mechanism of the nitrogen compounds over activated carbon was discussed on the basis of the structure‐performance correlation and the molecular simulation. © 2012 American Institute of Chemical Engineers AIChE J, 59: 1236–1244, 2013
Mutation‐based growth charts for SEDC and otherCOL2A1related dysplasias
Authors: Terhal Paulien A. , van Dommelen Paula , Le Merrer Martine , Zankl Andreas , Simon Marleen E.H. , Smithson Sarah F. , Marcelis Carlo , Kerr Bronwyn , Kinning Esther , Mansour Sahar , Hennekam Raoul C.M. , van der Hout Annemarie H. , Cormier‐Daire Valerie , Lund Allan M. , Goodwin Linda , Mégarbané André , Lees Melissa , Betz Regina C. , Tobias Edward S. , Coucke Paul , Mortier Geert R.
Published: July 2012

From data collected via a large international collaborative study, we have constructed a growth chart for patients with molecularly confirmed congenital spondylo‐epiphyseal dysplasia (SEDC) and otherCOL2A1related dysplasias. The growth chart is based on longitudinal height measurements of 79 patients with glycine substitutions in the triple‐helical domain of COL2A1. In addition, measurements of 27 patients with other molecular defects, such as arginine to cysteine substitutions, splice mutations, and mutations in the C‐terminal propeptide have been plotted on the chart. Height of the patients progressively deviate from that of normal children: compared to normal WHO charts, the mean length/height is −2.6 SD at birth, −4.2 SD at 5 years, and −5.8 SD in adulthood. The mean adult height (male and female combined) of patients with glycine substitutions in the triple‐helical region is 138.2 cm but there is a large variation. Patients with glycine to cysteine substitutions tend to cluster within the upper part of the chart, while patients with glycine to serine or valine substitutions are situated between +1 SD and −1 SD. Patients with carboxy‐terminal glycine substitutions tend to be shorter than patients with amino‐terminal substitutions, while patients with splice mutations are relatively tall. However, there are exceptions and specific mutations can have a strong or a relatively mild negative effect on growth. The observation of significant difference in adult height between affected members of the same family indicates that height remains a multifactorial trait even in the presence of a mutation with a strong dominant effect. © 2012 Wiley Periodicals, Inc.
The diagnostic challenge of progressive pseudorheumatoid dysplasia (PPRD): A review of clinical features, radiographic features, and WISP3 mutations in 63 affected individuals
Authors: Garcia Segarra Nuria , Mittaz Laureane , Campos‐Xavier Ana Belinda , Bartels Cynthia F. , Tuysuz Beyhan , Alanay Yasemin , Cimaz Rolando , Cormier‐Daire Valerie , Di Rocco Maja , Duba Hans‐Christoph , Elcioglu Nursel H. , Forzano Francesca , Hospach Toni , Kilic Esra , Kuemmerle‐Deschner Jasmin B. , Mortier Geert , Mrusek Sonja , Nampoothiri Sheela , Obersztyn Ewa , Pauli Richard M. , Selicorni Angelo , Tenconi Romano , Unger Sheila , Utine G. Eda , Wright Michael , Zabel Bernhard , Warman Matthew L. , Superti‐Furga Andrea , Bonafé Luisa
Published: July 2012

Progressive pseudorheumatoid dysplasia (PPRD) is a genetic, non‐inflammatory arthropathy caused by recessive loss of function mutations in WISP3 (Wnt1‐inducible signaling pathway protein 3; MIM 603400), encoding for a signaling protein. The disease is clinically silent at birth and in infancy. It manifests between the age of 3 and 6 years with joint pain and progressive joint stiffness. Affected children are referred to pediatric rheumatologists and orthopedic surgeons; however, signs of inflammation are absent and anti‐inflammatory treatment is of little help. Bony enlargement at the interphalangeal joints progresses leading to camptodactyly. Spine involvement develops in late childhood and adolescence leading to short trunk with thoracolumbar kyphosis. Adult height is usually below the 3rd percentile. Radiographic signs are relatively mild. Platyspondyly develops in late childhood and can be the first clue to the diagnosis. Enlargement of the phalangeal metaphyses develops subtly and is usually recognizable by 10 years. The femoral heads are large and the acetabulum forms a distinct “lip” overriding the femoral head. There is a progressive narrowing of all articular spaces as articular cartilage is lost. Medical management of PPRD remains symptomatic and relies on pain medication. Hip joint replacement surgery in early adulthood is effective in reducing pain and maintaining mobility and can be recommended. Subsequent knee joint replacement is a further option. Mutation analysis of WISP3 allowed the confirmation of the diagnosis in 63 out of 64 typical cases in our series. Intronic mutations in WISP3 leading to splicing aberrations can be detected only in cDNA from fibroblasts and therefore a skin biopsy is indicated when genomic analysis fails to reveal mutations in individuals with otherwise typical signs and symptoms. In spite of the first symptoms appearing in early childhood, the diagnosis of PPRD is most often made only in the second decade and affected children often receive unnecessary anti‐inflammatory and immunosuppressive treatments. Increasing awareness of PPRD appears to be essential to allow for a timely diagnosis. © 2012 Wiley Periodicals, Inc.
Recessive osteogenesis imperfecta: Clinical, radiological, and molecular findings
Authors: Rohrbach Marianne , Giunta Cecilia
Published: July 2012

Osteogenesis imperfecta (OI) or “brittle bone disease” is currently best described as a group of hereditary connective tissue disorders related to primary defects in type I procollagen, and to alterations in type I procollagen biosynthesis, both associated with osteoporosis and increased susceptibility to bone fractures. Initially, the autosomal dominant forms of OI, caused by mutations in either COL1A1 or COL1A2, were described. However, for decades, the molecular defect of a small percentage of patients clinically diagnosed with OI has remained elusive. It has been in the last 6 years that the genetic causes of several forms of OI with autosomal recessive inheritance have been characterized. These comprise defects of collagen chaperones, and proteins involved in type I procollagen assembly, processing and maturation, as well as proteins involved in the formation and homeostasis of bone tissue. This article reviews the recently characterized forms of recessive OI, focusing in particular on their clinical and molecular findings, and on their radiological characterisation. Clinical management and treatment of OI in general will be discussed, too. © 2012 Wiley Periodicals, Inc.
Ciliary disorder of the skeleton
Authors: Huber Celine , Cormier‐Daire Valerie
Published: July 2012

In the last 10 years, the primary cilia machinery has been implicated in more than a dozen disorders united as ciliopathies, including skeletal dysplasias, such as Jeune syndrome and short rib‐polydactyly type III. Indeed, primary cilia play a vital role in transduction of signals in the hedgehog pathway that is especially important in skeletal development. In this review, we focus on skeletal conditions belonging to the ciliopathy group: the short rib‐polydactyly group (SRPs) that includes Verma–Naumoff syndrome (SRP type III), Majewski syndrome (SRP type II), Jeune syndrome (ATD), as well as Ellis–van Creveld syndrome (EVC), the Sensenbrenner syndrome, and, finally, Weyers acrofacial dysostosis. Today, 10 different genes have been identified as responsible for seven “skeletal” ciliopathies. Mutations have been identified in dynein motor (DYNC2H1), in intraflagellar transport (IFT) complexes (IFT80, IFT122, IFT43, WDR35, WDR19, and TTC21B) as well as in genes responsible for the basal body (NEK1, EVC, and EVC2). The wide clinical variability observed for an individual ciliopathy gene supports the development of exome strategy specifically dedicated to cilia genes to identify mutations in this particularly heterogeneous group of disorders. © 2012 Wiley Periodicals, Inc.
Severe neurologic manifestations from cervical spine instability in spondylo‐megaepiphyseal‐metaphyseal dysplasia
Authors: Simon Marleen , Campos‐Xavier Ana Belinda , Mittaz‐Crettol Lauréane , Valadares Eugenia Ribeiro , Carvalho Daniel , Speck‐Martins Carlos Eduardo , Nampoothiri Sheela , Alanay Yasemin , Mihci Ercan , van Bever Yolande , Garcia‐Segarra Nuria , Cavalcanti Denise , Mortier Geert , Bonafé Luisa , Superti‐Furga Andrea
Published: July 2012

Spondylo‐megaepiphyseal‐metaphyseal dysplasia (SMMD; OMIM 613330) is a dysostosis/dysplasia caused by recessive mutations in the homeobox‐containing gene, NKX3‐2 (formerly known as BAPX1). Because of the rarity of the condition, its diagnostic features and natural course are not well known. We describe clinical and radiographic findings in six patients (five of which with homozygous mutations in the NKX3‐2 gene) and highlight the unusual and severe changes in the cervical spine and the neurologic complications. In individuals with SMMD, the trunk and the neck are short, while the limbs, fingers and toes are disproportionately long. Radiographs show a severe ossification delay of the vertebral bodies with sagittal and coronal clefts, missing ossification of the pubic bones, large round “balloon‐like” epiphyses of the long bones, and presence of multiple pseudoepiphyses at all metacarpals and phalanges. Reduced or absent ossification of the cervical vertebrae leads to cervical instability with anterior or posterior kinking of the cervical spine (swan neck‐like deformity, kyknodysostosis). As a result of the cervical spine instability or deformation, five of six patients in our series suffered cervical cord injury that manifested clinically as limb spasticity. Although the number of individuals observed is small, the high incidence of cervical spine deformation in SMMD is unique among skeletal dysplasias. Early diagnosis of SMMD by recognition of the radiographic pattern might prevent of the neurologic complications via prophylactic cervical spine stabilization. © 2012 Wiley Periodicals, Inc.
Revisiting dental fluctuating asymmetry in neandertals and modern humans
Authors: Barrett Christopher K. , Guatelli‐Steinberg Debbie , Sciulli Paul W.
Published: July 2012

Previous studies have suggested that Neandertals experienced greater physiological stress and/or were less capable of mitigating stress than most prehistoric modern human populations. The current study compares estimates of dental fluctuating asymmetry (DFA) for prehistoric Inupiat from Point Hope Alaska, the Late Archaic, and Protohistoric periods from Ohio and West Virginia, and a modern sample from Ohio to Neandertals from Europe and Southwest Asia. DFA results from developmental perturbation during crown formation and is thus an indicator of developmental stress, which previous studies have found to be higher in Neandertals than in several modern human populations. Here, we use recent methodological improvements in the analysis of fluctuating asymmetry suggested by Palmer and Strobeck (Annu Rev Ecol Syst 17 (1986) 391–421, Developmental instability: causes and consequences (2003a) v.1–v.36, Developmental instability: causes and consequences (2003b) 279–319) and compare the fit of Neandertal DFA Index values with those of modern humans. DFA estimates for each of the modern population samples exceeded measurement error, with the Inupiat exhibiting the highest levels of DFA for most tooth positions. All significant Neandertalz‐scores were positive, exceeding the estimates for each of the modern prehistoric groups. Neandertals exhibited the fewest significant differences from the Inupiat (9.2% of values are significant atP< 0.05), while for the other modern prehistoric groups more than 10% of the Neandertalz‐scores are significant atP< 0.05, more than 90% of these significant scores atP< 0.01. These results suggest that the Inupiat experienced greater developmental stress than the other prehistoric population samples, and that Neandertals were under greater developmental stress than all other prehistoric modern human samples. Am J Phys Anthropol 149:193–204, 2012. © 2012 Wiley Periodicals, Inc.
Preparation and characterization of polypyrrole/modified multiwalled carbon nanotube nanocomposites polymerized in situ in the presence of barium titanate
Authors: Moniruzzaman M. , Sahoo S. , Ghosh D. , Das C. K. , Singh R.
Published: July 2012

Polypyrrole (PPy) composites were prepared with both unmodified and amine‐modified multiwalled carbon nanotubes (MWCNTs) in the presence and absence of barium titanate (BaTiO3) by in situ oxidative polymerization. A uniform coating of PPy on the MWCNTs and BaTiO3 surfaces was confirmed by field emission scanning electron microscopy and high‐resolution transmission electron microscopy images. The structure of the pure and amine‐modified MWCNTs were identified by Fourier transform infrared spectroscopy. The incorporation of BaTiO3 enhanced the thermal stability and capacitance properties of the composites. The maximum specific capacitance and energy density values found for the PPy/amine‐modified MWCNT/BaTiO3 composites were 155.5 F/g and 21.6 W h/kg, respectively, at a scan rate of 10 mV/s. The maximum power density was found to be 385.7 W/kg for the same composite at a scan rate of 200 mV/s. Furthermore, the impedance spectra of the composites showed moderate capacitive behavior. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013
Curing studies of bisphenol a based bismaleimide and cloisite 15a nanoclay blends using differential scanning calorimetry and model‐free kinetics
Authors: Surender R. , Mahendran A. , Thamaraichelvan A. , Alam S. , Vijayakumar C. T.
Published: July 2012

Blends of 2,2‐bis[4‐(4‐maleimidophenoxy phenyl)]propane [bismaleimide (BMIX)] with different proportions (1, 2, 3, 4, 5, 7, and 9%) of the nanoclay Cloisite 15a were prepared with ultrasonication. Fourier transform infrared studies reveal the existence of interactions between the clay particles and the imide rings in BMIX. The difference in the melting characteristics and the decrease in the curing window caused by the incorporation of the clay particles in BMIX, as evidenced by detailed differential scanning calorimetry investigations, confirmed the existence of interactions between the nanoclay particles and BMIX molecules. The Flynn–Wall–Ozawa, Vyazovkin, and Friedman kinetics methods were used to calculate the activation energies (Ea's) for the curing of the BMIX materials.Eafor the polymerization varied, depending not only on the amount of clay loaded in the BMIX but also on the extent of the curing reaction. Because of the loss of interaction between the clay platelets and the imide rings of BMIX, a decrease inEaat higher reaction extents was noted when there was lower clay loadings (1–4% Cloisite 15a) in BMIX. A reversal in the previous behavior was noted at higher clay loadings (7 and 9% Cloisite 15a) in BMIX and was attributed to the restriction of the molecular mobility due to the presence of increased concentrations of clay platelets and the decreased availability of reaction sites for polymerization. These two opposing factors played were equal at the optimum level of Cloisite 15a loading (5%) in BMIX, which was reflected in the constancy ofEavariation noted with increasing reaction extent. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013
The LINDSAY Virtual Human Project: An immersive approach to anatomy and physiology
Authors: Tworek Janet K. , Jamniczky Heather A. , Jacob Christian , Hallgrímsson Benedikt , Wright Bruce
Published: July 2012

The increasing number of digital anatomy teaching software packages challenges anatomy educators on how to best integrate these tools for teaching and learning. Realistically, there exists a complex interplay of design, implementation, politics, and learning needs in the development and integration of software for education, each of which may be further amplified by the somewhat siloed roles of programmers, faculty, and students. LINDSAY Presenter is newly designed software that permits faculty and students to model and manipulate three‐dimensional anatomy presentations and images, while including embedded quizzes, links, and text‐based content. A validated tool measuring impact across pedagogy, resources, interactivity, freedom, granularity, and factors outside the immediate learning event was used in conjunction with observation, field notes, and focus groups to critically examine the impact of attitudes and perceptions of all stakeholders in the early implementation of LINDSAY Presenter before and after a three‐week trial period with the software. Results demonstrate that external, personal media usage, along with students' awareness of the need to apply anatomy to clinical professional situations drove expectations of LINDSAY Presenter. A focus on the software over learning, which can be expected during initial orientation, surprisingly remained after three weeks of use. The time‐intensive investment required to create learning content is a detractor from user‐generated content and may reflect the consumption nature of other forms of digital learning. Early excitement over new technologies needs to be tempered with clear understanding of what learning is afforded, and how these constructively support future application and integration into professional practice. Anat Sci Educ. © 2012 American Association of Anatomists.
Me‐BIPAM for the Synthesis of Optically Active 3‐Aryl‐3‐hydroxy‐2‐oxindoles by Ruthenium‐catalyzed Addition of Arylboronic Acids to Isatins
Authors: Yamamoto Yasunori , Yohda Masaaki , Shirai Tomohiko , Ito Hajime , Miyaura Norio
Published: July 2012

A chiral O‐linked C2‐symmetric bidentate phosphoramidite (Me‐BIPAM) was found to be efficient for the ruthenium‐catalyzed addition of arylboronic acids to isatins. Asymmetric synthesis of 3‐aryl‐3‐hydroxy‐2‐oxindoles by 1,2‐addition of arylboronic acids to isatins was carried out in the presence of [RuCl2(PPh3)3]/(R,R)‐Me‐BIPAM and KF, resulting in an enantioselectivity as high as 90 % ee. It was found that the reaction with N‐protected isatins proceeds with high yields and good enantioselectivities. The best protective groups on the nitrogen atom were different depending on the substituents on the aromatic ring. The use of a N‐benzyl group resulted in excellent enantioselectivities in many substrates compared with other groups.
Quantifying the role of atmospheric rivers in the interior western United States
Authors: Rutz Jonathan J. , Steenburgh W. James
Published: July 2012

Atmospheric rivers (ARs) have increasingly been recognized for their contribution to high‐impact weather and climate variability. A recent investigation based on observations located primarily in lowland valleys and basins of the western United States suggests that 10–50% of the total cool season (November to April) precipitation between water years 1998 and 2008 occurred on the day of and day following AR landfall (hereafter the AR fraction), as identified using Special Sensor Microwave Imager data. However, these results are based only on ARs crossing the North American west coast between 32.5°N and 52.5°N, which excludes those crossing the west coast of the Baja Peninsula. Here, we identify ARs in the ERA‐Interim reanalysis and examine the AR fraction at high‐elevation observational sites and in the NOAA/CPC Unified Daily Precipitation Analysis. At high‐elevation snowpack telemetry sites, we find good agreement with the AR fraction obtained previously for valley and basin locations. We also show that including ARs crossing the west coast of the Baja Peninsula (as far south as 24°N) substantially increases the AR fraction over the southwestern United States. Copyright © 2012 Royal Meteorological Society
Modeling credit portfolio derivatives, including both a default and a prepayment feature
Authors: Hieber Peter , Scherer Matthias
Published: July 2012

Apart from heteronomy exit events such as, for example credit default or death, several financial agreements allow policy holders to voluntarily terminate the contract. Examples include callable mortgages or life insurance contracts. For the contractual counterpart, the result is a cash‐flow uncertainty called prepayment risk. Despite the high relevance of this implicit option, only few portfolio models consider both a default and a cancellability feature. On a portfolio level, this is especially critical because empirical observations of the mortgage market suggest that prepayment risk is an important determinant for the pricing of mortgage‐backed securities. Furthermore, defaults and prepayments tend to occur in clusters, and there is evidence for a negative association between the two risks. This paper presents a realistic and tractable portfolio model that takes into account these observations. Technically, we rely on an Archimedean dependence structure. A suitable parameterization allows to fit the likelihood of default and prepayment clusters separately and accounts for the postulated negative interdependence. Moreover, this structure turns out to be tractable enough for real‐time evaluation of portfolio derivatives. As an application, the pricing of loan credit default swaps, an example of a portfolio derivative that includes a cancellability feature, is discussed. Copyright © 2012 John Wiley & Sons, Ltd.
Multivariate option pricing using copulae
Authors: Bernard Carole , Czado Claudia
Published: July 2012

The complexity of financial products significantly increased in the past 10 years. In this paper, we investigate the pricing of basket options and more generally of complex exotic contracts depending on multiple indices. Our approach assumes that the underlying assets evolve as dependent GARCH(1, 1) processes. The dependence among the assets is modeled using a copula based on pair‐copula constructions. Unlike most previous studies on this topic, we do not assume that the dependence observed between historical asset prices is similar to the dependence under the risk‐neutral probability. The method is illustrated with US market data on basket options written on two or three international indices. Copyright © 2012 John Wiley & Sons, Ltd.
Enzymatic transesterification monitored by an easy‐to‐use Fourier transform infrared spectroscopy method
Authors: Natalello Antonino , Sasso Francesco , Secundo Francesco
Published: July 2012

Transesterification of triglycerides with short chain alcohols is the key reaction in biodiesel production, in addition to other applications in chemical synthesis. However, it is crucial to optimize reaction conditions to make enzymatic transesterification a cost‐effective and competitive process. In this work, a new, easy Fourier transform infrared (FTIR) spectroscopic approach for monitoring the transesterification reaction is reported and compared with a gas‐chromatographic method. The concentration of the total methyl esters in the reaction mixture is determined from the peak intensity at ∼1435 cm–1 in the second derivatives of the FTIR absorption spectra using a linear regression calibration. Interestingly, we found that the use of second derivatives allows an accurate determination of the methyl esters without the interference of free fatty acids. Moreover, information on substrate hydrolysis can be obtained within the same measurement by the infrared absorption at ∼1709 cm–1. We applied this approach to monitor methanolysis and hydrolysis reactions catalyzed by different commercial lipases, which displayed different sensitivities to methanol inhibition. Therefore, the FTIR approach reported in this work represents a rapid, inexpensive, and accurate method to monitor enzymatic transesterification, requiring very limited sample preparation and a simple statistical analysis of the spectroscopic data.
RET expression and detection of KIF5B/RET gene rearrangements in Japanese lung cancer
Authors: Sasaki Hidefumi , Shimizu Shigeki , Tani Yoichi , Maekawa Masahiko , Okuda Katsuhiro , Yokota Keisuke , Shitara Masayuki , Hikosaka Yu , Moriyama Satoru , Yano Motoki , Fujii Yoshitaka
Published: July 2012

RET encodes the tyrosine kinase receptor of growth factors belonging to the glial‐derived neurotrophic factor family. Recently, RET gene rearrangements with N‐terminal of KIF5B gene were identified in lung adenocarcinomas from large‐scale sequencing. We investigated RET mRNA expression by real‐time reverse‐transcriptase polymerase chain reaction (RT‐PCR) assay using LightCycler, and KIF5B/RET gene rearrangements using newly established fluorescence in situ hybridization (FISH) analysis in surgically treated nonsmall cell lung cancer (NSCLC) cases. RET protein expression was also investigated by immunohistochemistry (IHC). This study included 157 surgically removed NSCLC cases for mRNA level analyses. The RET/β actin mRNA levels were not significantly different between lung cancer (6.359 ± 15.268) and adjacent normal lung tissues (8.205 ± 28.931, P = 0.6332). Tumor/normal (T/N) ratio of RET/β actin mRNA levels was not different within gender, stage, smoking status, and pathological subtypes. T/N ratio of RET/β actin mRNA levels was significantly higher in KIF5B/RET rearrangement samples (161.763 ± 123.488) than in wild‐type samples (5.9013 ± 17.148, P = 0.044). Although RET IHC positivity was not perfectly correlated with KIF5B/RET arrangement, we have detected the KIF5B/RET rearrangements using FISH analysis. Thus, we have successfully introduced FISH for diagnosing KIF5B/RET positive lung adenocarcinoma. This method facilitates the molecular evaluation for RET fusions and could be applicable in clinical practice to detect lung cancer that may be responsive to RET inhibitors.
Palladium‐Catalyzed Carbonylation of Chloroacetates to Afford Malonates: Controlling the Selectivity of the Product in a Buffer
Authors: Hu Jianglin , Zhang Qi , Guan Zhenhong , Gu Yanlong , Mo Wanling , Li Tao , Li Guangxing
Published: July 2012

We report an efficient process for the synthesis of diethyl malonate (DEM) and other malonates through the palladium‐catalyzed carbonylation of chloroacetates. Excellent selectivity (96 %) and yield (94 %) were obtained without the formation of Pd black. For the first time, a weakly alkaline buffer was used to control the selectivity for DEM in the reaction and we discuss the relationship between the buffer medium and selectivity in the reaction. The combination of anisole as the solvent and a Na2HPO4/NaH2PO4 buffer was beneficial for completely restraining the phase‐transfer‐catalyzed substitution of DEM with ethyl chloroacetate, as well as accommodating the proposed [(PPh3)2PdI]−[Bu4N]+ intermediate, by providing a suitable environment for its stable existence. We achieved the highest efficiency in the catalytic cycle by fine‐tuning the balance between the rates of oxidative addition and reductive elimination; moreover, we synthesized a recoverable heterogeneous polymer‐bound Pd catalyst in 85 % yield that could be reused without an appreciable loss in activity over four cycles.
Structure and Bonding Nature of the Strained Lewis Acid 3‐Methyl‐1‐boraadamantane: A Case Study Employing a New Data‐Analysis Procedure in Gas Electron Diffraction
Authors: Vishnevskiy Yury V. , Abaev Maxim A. , Rykov Anatolii N. , Gurskii Mikhail E. , Belyakov Pavel A. , Erdyakov Sergey Yu. , Bubnov Yuri N. , Mitzel Norbert W.
Published: July 2012

Base‐free 3‐methyl‐1‐boraadamantane was synthesized by starting from its known THF adduct, transforming it to a butylate‐complex withn‐butyllithium, cleaving the cage with acetyl chloride to give 3‐n‐butyl‐5‐methyl‐7‐methylene‐3‐borabicyclo[3.3.1]nonane and closing the cage again by reacting the latter with dicyclohexylborane. The identity of 3‐methyl‐1‐boraadamantane was proven by1H,11B and13C NMR spectroscopy and elemental analysis. The experimental equilibrium structure of the free 3‐methyl‐1‐boraadamantane molecules has been determined at 100 °C by using gas‐phase electron diffraction. For this structure determination, an improved method for data analysis has been introduced and tested: the structural refinement versus gas‐phase electron diffraction data (in terms of Cartesian coordinates) with a set of quantum‐chemically derived regularization constraints for the complete structure under optimization of a regularization constant, which maximizes the contribution of experimental data while retaining a stable refinement. The detailed analysis of parameter errors shows that the new approach allows obtaining more reliable results. The most important structural parameters are:re(B‐C)av=1.556(5) Å,${\angle }$e(C‐B‐C)av=116.5(2)°. The configuration of the boron atom is pyramidal with${\sum \angle }$(C‐B‐C)=349.4(4)°. The nature of bonding was analyzed further by applying the natural bond orbital (NBO) and atoms in molecules (AIM) approaches. The experimentally observed shortening of the BC bonds and elongation of the adjacent CC bonds can be explained by the σ(C‐C)→p(B) hyperconjugation model. Both NBO and AIM analyses predict that the BC bonds are significantly bent in the direction out of the cage.
Probing the Motional Behavior of Eumelanin and Pheomelanin with Solid‐State NMR Spectroscopy: New Insights into the Pigment Properties
Authors: Thureau Pierre , Ziarelli Fabio , Thévand André , Martin Rachel W. , Farmer Patrick J. , Viel Stéphane , Mollica Giulia
Published: July 2012

Melanin is the most widespread pigment in the animal kingdom. Despite its importance, its detailed structure and overall molecular architecture remain elusive. Both eumelanin (black) and pheomelanin (red) occur in the human body. These two melanin compounds show very different responses to UV‐radiation exposure, which could relate to their microscopic features. Herein, the structural properties and motional behavior of natural eu‐ and pheomelanin extracted from black and red human hair are investigated by means of solid‐state NMR spectroscopy. Several 1D and 2D NMR spectroscopic techniques were combined to highlight the differences between the two forms of the pigment. The quantitative analysis of the 1H NMR wide‐line spectra extracted from 2D 1H–13C LG‐WISE experiments revealed the presence of two dynamically distinguishable components in both forms. Remarkably, the more mobile fraction of the pigment showed a higher mobility with respect to the proteinaceous components that coexist in the melanosome, which is particularly evident for the red pigment. An explanation of the observed effects takes into account the different architecture of the proteinaceous matrix that constitutes the physical substrate onto which melanin polymerizes within the eu‐ and pheomelanosomes. Further insight into the molecular structure of the more mobile fraction of pheomelanin was also obtained by means of the analysis of 2D 1H–13C INEPT experiments. Our view is that not only structural features inherent in the pure pigment, but also the role of the matrix structure in defining the overall melanin supramolecular arrangement and the resulting dynamic behavior of the two melanin compounds should be taken into account to explain their functions. The reported results could pave a new way toward the explanation of the molecular origin of the differences in the photoprotection activity displayed by black and red melanin pigments.
Consequences of the One‐Electron Reduction and Photoexcitation of Unsymmetric Bis‐imidazolium Salts
Authors: Gierz Verena , Melomedov Jascha , Förster Christoph , Deißler Christine , Rominger Frank , Kunz Doris , Heinze Katja
Published: July 2012

Coupling of uronium salts with in situ generated N‐heterocyclic carbenes provides straightforward access to symmetrical [4]2+ and unsymmetrical bis‐imidazolium salts [6]2+ and [9]2+. As indicated by cyclic and square‐wave voltammetry, [6]2+ and [9]2+ can be (irreversibly) reduced by one electron. The initially formed radicals [6].+ and [9].+ undergo further reactions, which were probed by EPR spectroscopy and density functional calculations. The final products of the two‐electron reduction are the two carbenes. Upon irradiation with UV light both [6]2+ and [9]2+ emit at room temperature in solution but with dramatically different characteristics. The different fluorescence behavior is analyzed by emission spectroscopy and interpreted by using time‐dependent density functional calculations as largely due to different excited‐state dynamics of [6]2+ and [9]2+. The geometries of both radicals [6].+ and [9].+ and excited states {[6]2+}* and {[9]2+}* are substantially different from those of the parent ground‐state molecules.
Toward Ultralow‐Bandgap Liquid Crystalline Semiconductors: Use of Triply Fused Metalloporphyrin Trimer–Pentamer as Extra‐large π‐Extended Mesogenic Motifs
Authors: Tanaka Seiya , Sakurai Tsuneaki , Honsho Yoshihito , Saeki Akinori , Seki Shu , Kato Kenichi , Takata Masaki , Osuka Atsuhiro , Aida Takuzo
Published: July 2012

In contrast with their dimeric homologue, triply fused zinc porphyrin trimer–pentamer, as extra‐large π‐extended mesogens, assemble into columnar liquid crystals (LCs) when combined with 3,4,5‐tri(dodecyloxy)phenyl side groups (3 PZn–5 PZn, Figure 1). Their LC mesophases develop over a wide temperature range, namely, 41–280 °C (on heating) for 5 PZn, and all adopt an oblique columnar geometry, typically seen in columnar LC materials involving strong mesogenic interactions. These LC materials are characterized by their wide light‐absorption windows from the entire visible region up to a near infrared (NIR) region. Such ultralow‐bandgap LC materials are chemically stable and serve as hole transporters, in which 5 PZn gives the largest charge carrier mobility (2.4×10−2 cm V−1 s−1) among the series. Despite a big dimensional difference, they coassemble without phase separation, in which the resultant LC materials display essentially no deterioration of the intrinsic conducting properties.
Discovery of BAY 94‐8862: A Nonsteroidal Antagonist of the Mineralocorticoid Receptor for the Treatment of Cardiorenal Diseases
Authors: Bärfacker Lars , Kuhl Alexander , Hillisch Alexander , Grosser Rolf , Figueroa‐Pérez Santiago , Heckroth Heike , Nitsche Adam , Ergüden Jens‐Kerim , Gielen‐Haertwig Heike , Schlemmer Karl‐Heinz , Mittendorf Joachim , Paulsen Holger , Platzek Johannes , Kolkhof Peter
Published: July 2012

Aldosterone is a hormone that exerts manifold deleterious effects on the kidneys, blood vessels, and heart which can lead to pathophysiological consequences. Inhibition of the mineralocorticoid receptor (MR) is a proven therapeutic concept for the management of associated diseases. Use of the currently marketed MR antagonists spironolactone and eplerenone is restricted, however, due to a lack of selectivity in spironolactone and the lower potency and efficacy of eplerenone. Several pharmaceutical companies have implemented programs to identify drugs that overcome the known liabilities of steroidal MR antagonists. Herein we disclose an extended SAR exploration starting from cyano‐1,4‐dihydropyridines that were identified by high‐throughput screening. Our efforts led to the identification of a dihydronaphthyridine, BAY 94‐8862, which is a potent, selective, and orally available nonsteroidal MR antagonist currently under investigation in a clinical phase II trial.