bluuebunny/crossref_metadata_2025 huggingface dataset:
Wage Labor
Authors: Katz‐Fishman Walda , Scott Jerome
Published: March 2012

Wage labor is the process by which workers sell their labor power to capitalists, that is, their employers, in exchange for wages, which they use to purchase the necessaries of life in the market. Wage labor becomes the predominant form of labor with the rise of capitalism, markets, commodity production, and nation‐states in the modern era. Over the capitalist epoch, wage labor is employed in a production process that transitions from small‐scale manufacturing – using hand tools in factories – to large‐scale machine‐based industry, to electronic‐based automated production and new aspects of capitalist globalization. The unique quality of labor power is that it is the only commodity that produces new value; and, as wage labor within capitalism, this means producing surplus value and thus profit for capital. This relationship between capital and labor is fraught with contradictions (Marx 1967; Marx 1986). Under the current conditions of twenty‐first century globalization, these contradictions are intensifying and giving rise to deepening systemic crises and various forms of struggle (Davis et al. 1997; Amin 2003; Robinson 2004; Katz‐Fishman et al. 2005; Berberoglu 2009).
Design to Self‐Assembly
Authors: Tibbits Skylar
Published: March 2012

The increasing power of design software, the widespread availability of digital fabrication and growing complexity of our built environment are in stark contrast to the inefficient techniques that currently plague the construction industry. Today's processes of assembly can be fundamentally re‐imagined by looking at biological systems that are building structures with far more complexity, information capacity and assembly instructions than even the most advanced structures possible with current technologies. Skylar Tibbits explains that the key ingredient embedded within these natural systems is self‐assembly. He outlines four principles for designing systems that build themselves, and shows a number of projects that demonstrate first steps towards this new mode of architectural production. Copyright © 2012 John Wiley & Sons, Ltd.
Aggregate Structures: Material and Machine Computation of Designed Granular Substances
Authors: Dierichs Karola , Menges Achim
Published: March 2012

In inanimate nature, large masses of granular substances are in constant processes of formation through perpetual cycles of erosion and accretion. What if architecture was to emulate this behaviour and allow for its own continuous reconfiguration? Karola Dierichs and Achim Menges establish the notion of an ‘aggregate architecture’. Composed of large numbers of unbound yet designed granules, aggregates are based on a fundamentally different logic of construction. In contrast to assembly systems, aggregates materially compute their overall constructional configuration and shape as spatiotemporal behavioural patterns, with an equal ability for both: the stable character of a solid material and the rapid reconfigurability of a fluid. Copyright © 2012 John Wiley & Sons, Ltd.
Living Systems: Designing Growth in Baubotanik
Authors: Ludwig Ferdinand , Schwertfreger Hannes , Storz Oliver
Published: March 2012

Baubotanik – the construction method that uses living plants for load bearing in architectural structures – provides a surprising ability to anticipate the latent convergence of non‐living and living systems in architecture. Through interdisciplinary research by architects, engineers and biologists it aims to synthesise architectural qualities, constructive requirements and biological properties in living structures. In this article, Ferdinand Ludwig, Hannes Schwertfeger and Oliver Storz of the Baubotanik research group at the Institute for Architectural Theory and Design (IGMA) at the University of Stuttgart explain how living and non‐living building elements can be designed to develop into vegetal‐technical compound structures. Copyright © 2012 John Wiley & Sons, Ltd.
Programming Matter
Authors: Oxman Neri
Published: March 2012

A direct parallel can be made between the Modernist separation of form, structure and material and the more recent tripartite division in digital processes of modelling, analysis and fabrication, which has resulted in the predominance of geometric‐driven form‐generation. Today, though, design culture is experiencing a shift to a new level of material awareness. Inspired by nature's strategies where form‐generation is driven by maximal performance with minimal resources through local material property variation, Neri Oxman investigates a novel design approach to digital fabrication that offers the potential to program physical matter. Copyright © 2012 John Wiley & Sons, Ltd.
Material Articulation: Computing and Constructing Continuous Differentiation
Authors: Ceccato Cristiano
Published: March 2012

Free‐form geometric designs make use of continuously differentiated components that exist within a multidimensional envelope of material performance, fabrication capabilities, logistics and cost. In this article, Cristiano Ceccato explains how geometric form‐rationalisation and analysis of constructability at the functional as well as the computational level form the basis for achieving advanced designs in terms of articulation of material through mass‐customised industrial production. Taking examples from the current work of Zaha Hadid Architects (ZHA), he presents a necessarily evolving framework of computational design and associated practice of architecture that is attempting to close the gaps between computational design, digitally controlled manufacturing and evolving mechanisms of contemporary construction and project delivery. Copyright © 2012 John Wiley & Sons, Ltd.
The Role of Additive Manufacturing and Physiomimetic Computational Design for Digital Construction
Authors: Soar Rupert , Andreen David
Published: March 2012

The recent adoption of the term additive manufacturing (AM) to describe a broad range of digital ‘layer by layer’ fabrication techniques comes 20 years since its inception and more than 10 years since architectural practices engaged with the technology for making prototypes and models. Soon this technology will join existing CNC subtractive and formative processes within the volume and mass‐market sectors, where design complexity and increased functionality result in competitive advantage. It is also about a decade since researchers proposed additive manufacturing for construction. Rupert Soar and David Andreen introduce here the different construction‐scale additive manufacturing systems currently in development. If linked to physiomimetic computational design strategies, these technologies provide novel possibilities for addressing architecture's manufacturing challenges in the face of energy expenditure, material resources and environmental impact. Copyright © 2012 John Wiley & Sons, Ltd.
Distinguishing Between the Drawn and the Made
Authors: Sheil Bob
Published: March 2012

Here Bob Sheil, Director of Technology and Computing at the Bartlett School of Architecture and co‐organiser of the 2011 Fabricate Conference at UCL, pulls back on the rush towards material computation. With the blurring of the projected image and the constructed artefact, there is the very real danger of reducing ‘architectural production to a systematic industrial exercise’. This fails to recognise the extent to which ideas and performance are transformed, developed and refined through the very process of making. Copyright © 2012 John Wiley & Sons, Ltd.
Lone‐Pair‐Induced Covalency as the Cause of Temperature‐ and Field‐Induced Instabilities in Bismuth Sodium Titanate
Authors: Schütz Denis , Deluca Marco , Krauss Werner , Feteira Antonio , Jackson Tim , Reichmann Klaus
Published: March 2012

Bismuth sodium titanate (BNT)‐derived materials have seen a flurry of research interest in recent years because of the existence of extended strain under applied electric fields, surpassing that of lead zirconate titanate (PZT), the most commonly used piezoelectric. The underlying physical and chemical mechanisms responsible for such extraordinary strain levels in BNT are still poorly understood, as is the nature of the successive phase transitions. A comprehensive explanation is proposed here, combining the short‐range chemical and structural sensitivity of in situ Raman spectroscopy (under an applied electric field and temperature) with macroscopic electrical measurements. The results presented clarify the causes for the extended strain, as well as the peculiar temperature‐dependent properties encountered in this system. The underlying cause is determined to be mediated by the complex‐like bonding of the octahedra at the center of the perovskite: a loss of hybridization of the 6s2bismuth lone pair interacting with the oxygen p‐orbitals occurs, which triggers both the field‐induced phase transition and the loss of macroscopic ferroelectric order at the depolarization temperature.
Lipid‐Containing Polymer Vesicles with pH/Ca2+‐Ion‐Manipulated, Size‐Selective Permeability
Authors: Huang Wen‐Chia , Chiang Wen‐Hsuan , Lin Su‐Jen , Lan Yu‐Jen , Chen Hsin‐Lung , Chern Chorng‐Shyan , Chiu Hsin‐Cheng
Published: March 2012

Polymeric vesicles attained from the self‐assembly of distearin (a diacylglycerol lipid)‐conjugated poly(acrylic acid) (PAAc) with various distearin contents in the aqueous phase show the capability of control over the vesicular‐wall permeability to hydrophilic solutes of varying sizes by a simple manipulation of the external pH. The pH sensitivity of the vesicle membranes in size‐selective permeability is largely dependent upon the lipid content of copolymer. By the addition of CaCl2 in aqueous vesicle suspensions, the pH‐evolved assembly structure and the membrane permeability can be immobilized with promoted resistance to further pH alteration, along with an additional counterion screening effect that reduces the pH required for the onset of polar solutes of certain sizes to pass through the membranes. Small‐angle X‐ray scattering (SAXS) measurements of the vesicle structure in the aqueous phase indicate that the pH‐regulated permeability to polar solutes is virtually governed by the extent of hydration and swelling of the vesicle membranes, and the lipid residues within each vesicle wall are packed into the ≈4–5 repeating lamellar islet structure surrounded by PAAc segments.
Microfabricated Biomaterials for Engineering 3D Tissues
Authors: Zorlutuna Pinar , Annabi Nasim , Camci‐Unal Gulden , Nikkhah Mehdi , Cha Jae Min , Nichol Jason W. , Manbachi Amir , Bae Hojae , Chen Shaochen , Khademhosseini Ali
Published: March 2012

Mimicking natural tissue structure is crucial for engineered tissues with intended applications ranging from regenerative medicine to biorobotics. Native tissues are highly organized at the microscale, thus making these natural characteristics an integral part of creating effective biomimetic tissue structures. There exists a growing appreciation that the incorporation of similar highly organized microscale structures in tissue engineering may yield a remedy for problems ranging from vascularization to cell function control/determination. In this review, we highlight the recent progress in the field of microscale tissue engineering and discuss the use of various biomaterials for generating engineered tissue structures with microscale features. In particular, we will discuss the use of microscale approaches to engineer the architecture of scaffolds, generate artificial vasculature, and control cellular orientation and differentiation. In addition, the emergence of microfabricated tissue units and the modular assembly to emulate hierarchical tissues will be discussed.
Core Scaffold‐Inspired Concise Synthesis of Chiral Spirooxindole‐Pyranopyrimidines with Broad‐Spectrum Anticancer Potency
Authors: Jiang Xianxing , Sun Yulong , Yao Jia , Cao Yiming , Kai Ming , He Ning , Zhang Xiaoyuan , Wang Yiqing , Wang Rui
Published: March 2012

Due to the lack of tumor‐specific anticancer agents, the discovery and development of new types of highly selective anticancer agents is still a very urgent topic. Herein, we present our contribution to concise construction of novel chiral spirooxindole‐type pyranopyrimidines exhibiting a unique profile of biological activities. We have found that this new type of spiro alkaloid could inhibit the proliferation of various cancer cells in a preliminary biological evaluation. These findings suggested that spirooxindole‐type pyranopyrimidines, developed by an asymmetric Michael/cyclization strategy, can potentially serve as a new kind of anticancer candidate.
Enantioselective Synthesis of Highly Functionalized Trifluoromethyl‐Bearing Cyclopentenes: Asymmetric [3+2] Annulation of Morita–Baylis–Hillman Carbonates with Trifluoroethylidenemalonates Catalyzed by Multifunctional Thiourea‐Phosphines
Authors: Deng Hong‐Ping , Wei Yin , Shi Min
Published: March 2012

On the basis of the design and synthesis of multifunctional thiourea‐phosphines, a catalytic method for the asymmetric [3+2] annulation of Morita–Baylis–Hillman carbonates with trifluoroethylidenemalonates has been developed, affording highly functionalized trifluoromethyl‐bearing cyclopentenes in excellent yields, high diastereoselectivities and enantioselectivities under mild conditions.
Dental health in Northern Chile's Atacama oases: Evaluating the Middle Horizon (AD 500–1000) impact on local diet
Authors: Hubbe Mark , Torres‐Rouff Christina , Neves Walter Alves , King Laura M. , Da‐Gloria Pedro , Costa Maria Antonietta
Published: March 2012

As one of the few areas apt for horticulture in Northern Chile's arid landscape, the prehistory of the Atacama oases is deeply enmeshed with that of the inter‐regional networks that promoted societal development in the south central Andes. During the Middle Horizon (AD 500–1000), local populations experienced a cultural apex associated with a substantial increase in inter‐regional interaction, population density, and quantity and quality of mortuary assemblages. Here, we test if this cultural peak affected dietary practices equally among the distinct local groups of this period. We examine caries prevalence and the degree of occlusal wear in four series recovered from three cemeteries. Our results show a reduction in the prevalence of caries for males among an elite subsample from Solcor 3 and the later Coyo 3 cemeteries. Dental wear tends to increase over time with the Late Middle Horizon/Late Intermediate Period cemetery of Quitor 6 showing a higher average degree of wear. When considered in concert with archaeological information, we concluded that the Middle Horizon was marked by dietary variability wherein some populations were able to obtain better access to protein sources (e.g., camelid meat). Not all members of Atacameño society benefited from this, as we note that this dietary change only affected men. Our results suggest that the benefits brought to the San Pedro oases during the Middle Horizon were not equally distributed among local groups and that social status, relationship to the Tiwanaku polity, and interment in particular cemeteries affected dietary composition. Am J Phys Anthropol, 2012. © 2012 Wiley Periodicals, Inc.
Total Syntheses of the Elusive Welwitindolinones with Bicyclo[4.3.1] Cores
Authors: Huters Alexander D. , Styduhar Evan D. , Garg Neil K.
Published: March 2012

The welwitindolinones with bicyclo[4.3.1] cores are a class of natural products that have attracted tremendous interest from the synthetic community because of their fascinating structures and promising biological profiles. More than 15 research groups worldwide have reported progress toward these elusive natural products. This Minireview describes contemporary studies aimed at the total synthesis of these challenging targets, in addition to the two recently completed syntheses of welwitindolinones with bicyclo[4.3.1] cores reported by Rawal and Garg in 2011. Both of the completed efforts rely on C4C11 bond constructions to access the congested bicyclic framework of these elusive natural products.
Reaction of “Non‐Symmetrical” 1,2,4‐Trithiolanes with [(phosphane)Pt0(η2‐nbe)] Complexes
Authors: Weisheit Thomas , Kriltz Antje , Görls Helmar , Mlostoń Grzegorz , Imhof Wolfgang , Weigand Wolfgang
Published: March 2012

Two unsymmetrical 1,2,4‐trithiolanes (1d and 1e) were reacted with [Pt0(PPh3)2(η2‐nbe)] (6; nbe=norborn‐2‐ene) and [Pt0(dppn)(η2‐nbe)] (11; dppn=1,8‐bis(diphenylphosphanyl)naphthalene)), respectively. Their treatment with compound 6 resulted in the formation of six‐membered platinacycles of type 7, which selectively underwent fragmentation into dithiolato complexes and thiobenzophenone (4b). The isolation of the first stable C‐substituted member of this class of compounds (i.e., compound 7e) permitted kinetic studies of this process by using UV/Vis spectroscopy. These results, together with DFT calculations, allowed us to propose a mechanism for the reactions of compound 6 with 1,2,4‐trithiolanes. In contrast, similar treatment of compound 11 with compounds 1d and 1e at room temperature did not result in any reaction. Heating the appropriate samples to 110 °C led to the formation of dithiolato complexes and η2‐thioketone compounds, thus pointing to a thermally induced [3+2]‐cycloreversion of the heterocycles as an initial step of the reaction.
A stochastic multi‐period investment selection model to optimize strategic railway capacity planning
Authors: Lai Yung‐Cheng , Shih Mei‐Cheng
Published: March 2012

North American Freight Railroads are approaching the limits of practical capacity because of substantial future demand. In this research, we develop a Stochastic Multi‐period Investment Selection Model (S‐MISM) to assist railroads best allocate their capital investments in the long‐term strategic capacity planning process. The novel optimization framework uses stochastic programming and Benders decomposition and provides a means to cope with unfulfilled demand and demand uncertainty in a long‐term multi‐period investment selection problem. S‐MISM can determine which portions of a rail network need to be upgraded with what kind of expansion options at each defined period in the planning horizon. Experimental results show that the inclusion of demand uncertainty results in a better and more robust capacity plan. Using this decision support tool will help railroads maximize their return from capacity expansion projects and minimize the risk in strategic capacity planning subject to demand uncertainty. Copyright © 2012 John Wiley & Sons, Ltd.
Genetic variants of organic cation transporter 1 (OCT1) and OCT2 significantly reduce lamivudine uptake
Authors: Choi Min‐Koo , Song Im‐Sook
Published: March 2012

The study sought to investigate the effect of genetic variants of OCT1 (OCT1‐P283L and ‐P341L) and OCT2 (OCT2‐T199I, ‐T201M and ‐A270S), which were identified in a Korean population, on the transport of lamivudine in vitro and to compare the substrate dependent effects of OCT1 and OCT2 variants with 1‐methyl‐4‐phenylpyridinium (MPP+), tetraethyl ammonium (TEA), metformin and lamivudine as substrates for these transporters. When the transport kinetics of lamivudine uptake in oocytes overexpressing OCT1 and OCT2 wild‐type (WT) and variant proteins were measured, lamivudine uptake mediated by OCT1‐WT was saturable, and uptake was decreased in oocytes expressing OCT1‐P283L and ‐P341L variants compared with that in OCT1‐WT. The Clint of lamivudine in oocytes expressing OCT1‐P283L was decreased by 85.1% compared with OCT1‐WT, whereas it was decreased by 48.7% in oocytes expressing OCT1‐P341L. The Clint of lamivudine in oocytes expressing OCT2‐T199I, ‐T201M and ‐A270S was decreased by 86.2%, 88.9% and 73.6%, respectively, compared with OCT2‐WT. When comparing various substrates such as MPP+, TEA, metformin and lamivudine, the effects of the OCT1 genetic polymorphisms on their uptake were not identical. However, contrary to the case of OCT1, the uptake of MPP+, TEA, metformin and lamivudine in oocytes expressing OCT2‐T199I, ‐T201M and ‐A270S variants was decreased significantly compared with that in oocytes expressing OCT2‐WT. In conclusion, the effect of genetic variations of OCT1 and OCT2 on the uptake of MPP+, TEA, metformin and lamivudine was substrate‐dependent. Copyright © 2012 John Wiley & Sons, Ltd.
Fluorescence correlation spectroscopy
Authors: Ries Jonas , Schwille Petra
Published: March 2012

Fluorescence correlation spectroscopy (FCS) is a powerful technique to measure concentrations, mobilities, and interactions of fluorescent biomolecules. It can be applied to various biological systems such as simple homogeneous solutions, cells, artificial, or cellular membranes and whole organisms. Here, we introduce the basic principle of FCS, discuss its application to biological questions as well as its limitations and challenges, present an overview of novel technical developments to overcome those challenges, and conclude with speculations about the future applications of fluorescence fluctuation spectroscopy.
Macromolecular structure modeling from 3D EM using VolRover 2.0
Authors: Zhang Qin , Bettadapura Radhakrishna , Bajaj Chandrajit
Published: March 2012

We review tools for structure identification and model‐based refinement from three‐dimensional electron microscopy implemented in our in‐house software package, VOLROVER 2.0. For viral density maps with icosahedral symmetry, we segment the capsid, polymeric, and monomeric subunits using techniques based on automatic symmetry detection and multidomain fast marching. For large biomolecules without symmetry information, we again use our multidomain fast‐marching method with manual or fit‐based multiseeding to segment meaningful substructures. In either case, we subject the resulting segmented subunit to secondary structure detection when the EM resolution is sufficiently high, and rigid‐body structure fitting when the corresponding X‐ray structure is available. Secondary structure elements are identified by three techniques: our earlier volume‐based and boundary‐based skeletonization methods as well as a new method, currently in development, based on solving the grassfire flow equation. For rigid‐body fitting, we adapt our earlier fast Fourier‐based correlation scheme F2Dock. Our reported segmentation, secondary structure elements identification, and rigid‐body fitting techniques, implemented in VOLROVER 2.0 are applied to the PSB 2011 cryo‐EM modeling challenge data, and our results are briefly compared to similar results submitted from other research groups. The comparisons show that our techniques are equally capable of segmenting relatively accurate subunits from a viral or protein assembly, and that high segmentation quality leads in turn to higher‐quality results of secondary structure elements identification and correlation‐based rigid‐body fitting. © 2012 Wiley Periodicals, Inc. Biopolymers 97: 709–731, 2012.
Assessment of Accused Juvenile Sex Offenders in Germany: A Comparison of Five Different Measures
Authors: Klein Verena , Yoon Dahlnym , Briken Peer , Turner Daniel , Spehr Aranke , Rettenberger Martin
Published: March 2012

The present study examines the relationship between risk and protective factors among young alleged sexual offenders (N = 66) in pre‐trial and pre‐treatment settings. For risk assessment purposes, the Screening Tool for the Assessment of Young Sexual Offenders’ Risk (STAYSOR), the Structured Assessment of Violence Risk in Youth (SAVRY), and the Structured Assessment of Protective Factors for violence risk (SAPROF) were used. Psychopathological indicators measured with the Basis Raads Onderzoek (BARO) and the German adaption of the Reynolds Adolescent Adjustment Screening Inventory (RAASI) were used to examine the relationship between the risk assessment scales and instruments measuring risk‐relevant psychopathological constructs. Risk and protective factors were significantly negatively correlated. Psychopathological measures were positively correlated with risk factors and negatively with protective factors. Although further studies on the predictive validity of the instruments are needed, the results of the present explorative pilot study indicate that the use of all five instruments may be clinically meaningful for the assessment of young persons who are at risk of sexual offending. Copyright © 2012 John Wiley & Sons, Ltd.
Kinetic and Stoichiometric Characterisation of Streptavidin‐Binding Aptamers
Authors: Ruigrok Vincent J. B. , van Duijn Esther , Barendregt Arjan , Dyer Kevin , Tainer John A. , Stoltenburg Regina , Strehlitz Beate , Levisson Mark , Smidt Hauke , van der Oost John
Published: March 2012

Aptamers are oligonucleotide ligands that are selected for high‐affinity binding to molecular targets. Only limited knowledge relating to relations between structural and kinetic properties that define aptamer–target interactions is available. To this end, streptavidin‐binding aptamers were isolated and characterised by distinct analytical techniques. Binding kinetics of five broadly similar aptamers were determined by surface plasmon resonance (SPR); affinities ranged from 35–375 nM with large differences in association and dissociation rates. Native mass spectrometry showed that streptavidin can accommodate up to two aptamer units. In a 3D model of one aptamer, conserved regions are exposed, strongly suggesting that they directly interact with the biotin‐binding pockets of streptavidin. Mutational studies confirmed both conserved regions to be crucial for binding. An important result is the observation that the most abundant aptamer in our selections is not the tightest binder, emphasising the importance of having insight into the kinetics of complex formation. To find the tightest binder it might be better to perform fewer selection rounds and to focus on post‐selection characterisation, through the use of complementary approaches as described in this study.
Engagement in psychosocial treatment: Its relationship to outcome and care pathway progress for women in medium‐secure settings
Authors: Long Clive , Dolley Olga , Hollin Clive
Published: March 2012

Background

Engaging patients in treatment in secure settings is a major challenge. Engagement is associated with a shorter length of stay, whereas treatment non‐completion is associated with an increased risk of recidivism.

Aims

The aims of this study were to assess differences between high and low treatment attendees in a women's medium secure unit and to compare progress over the course of their stay.

Methods

Sixty consecutive admissions to a women's medium secure unit were classified into high and low treatment attendee groups. The two groups were compared in terms of risk behaviours and psychometric measures of symptomatology, impulsivity and personality.

Results

High treatment attendees had a shortened length of stay, showed less disturbed behaviour and made more progress in terms of a reduction in symptoms overall and traumatic stress symptoms specifically. Low treatment attendees were more likely to have a diagnosis of schizophrenia/schizotypal illness than personality disorder, less likely to be impulsive and more likely to have scores indicative of severe disorder on the personality subscales of the Millon Clinical Multiaxial Inventory—III.

Conclusion

Attendance at groups in this medium security unit had clear advantages for patients and potential cost savings for services and the community, but we found a subgroup of women who found it difficult to attend. Given the small sample size, we advocate replication, but our findings suggest the following:

Implications for practice

development of motivational interventions to help patients make a therapeutic alliance

more accurate assessment of treatment readiness, to avoid mistimed interventions that are counterproductive

more effective deployment of milieu therapeutic approaches to stabilise behaviour at an early stage of hospitalisation

abandonment of a ‘one size fits all’ approach to groups for mixed patient populations. More ‘customised’ approaches would allow more appropriate ‘pacing’ of treatment and adaptations of interventions according to need during the treatment course.

Copyright © 2012 John Wiley & Sons, Ltd.
Novel Composite Spherical Granulates with Catalytic Outer Layer and Improved Conversion Efficiency and Selectivity
Authors: Schmidt F. , Klemm H. , Schönfeld K. , Gerds A. , Hungerbach W. , Van Lookeren Campagne C. J. , Kaskel S.
Published: March 2012

The granulation procedure of a catalyst powder is a crucial step in designing a high‐quality catalyst granulate for industrial applications. New granulation processes have been developed that make it possible to form granulates with a very narrow particle size distribution and high sphericity. The innovative granulation techniques offer a great potential to produce layered catalysts with inert cores and an active shell. The novel spherical granules consist of an inexpensive inert core coated with an active catalyst material. New core shell granules with an accurately designed spherical geometry have been synthesized and compared to conventional homogeneous spherical granules of the same shape. The conversion of methanol to olefins has been used as a test reaction to validate the efficiency of these promising granulates.
Full Characterization of Colloidal Solutions of Long‐Alkyl‐Chain‐Amine‐Stabilized ZnO Nanoparticles by NMR Spectroscopy: Surface State, Equilibria, and Affinity
Authors: Coppel Yannick , Spataro Grégory , Pagès Carole , Chaudret Bruno , Maisonnat André , Kahn Myrtil L.
Published: March 2012

Full NMR characterization of ZnO nanoparticles (NPs) stabilized by various amines (hexadecylamine, dodecylamine, and octylamine) in C7D8 demonstrated that the surface of this apparently simple system was very complex. Using different NMR spectroscopic techniques (1H, PGSE‐NMR, diffusion‐filtered 1H NMR, NOESY, ROESY), we observed at least three different modes of interaction of the amines at the surface of the NPs, in thermodynamic equilibrium with the free amines, the relative populations of which varied with their concentration. The first mode corresponded to a strong interaction between a small amount of amine and the ZnO NPs (kdesorp≈13 s−1). The second mode corresponded to a weak interaction between the amines and the surface of the ZnO NPs (koff(2)≈50–60 s−1). The third, and weakest, mode of interaction corresponded to the formation of a second ligand shell by the amine around the NPs that was held together through van der Waals interactions (koff(1)≈25×105 s−1). The second and third modes were in fast exchange on the NMR timescales with the free amines. The strongly interacting amines at the NPs surface (first mode) were in slow exchange with the other modes. A complex hydrogen‐bonding network at the NPs surface was also observed, which did not only involve the coordinated amine but also THF and water molecules that remained from the synthesis.
Amphiphilic Schiff Base Organogels: Metal‐Ion‐Mediated Chiral Twists and Chiral Recognition
Authors: Jin Qingxian , Zhang Li , Zhu Xuefeng , Duan Pengfei , Liu Minghua
Published: March 2012

New amphiphilic gelators that contained both Schiff base and L‐glutamide moieties, abbreviated as o‐SLG and p‐SLG, were synthesized and their self‐assembly in various organic solvents in the absence and presence of metal ions was investigated. Gelation test revealed that o‐SLG formed a thermotropic gel in many organic solvents, whilst p‐SLG did not. When metal ions, such as Cu2+, Zn2+, Mg2+, Ni2+, were added, different behaviors were observed. The addition of Cu2+ induced p‐SLG to from an organogel. In the case of o‐SLG, the addition of Cu2+ and Mg2+ ions maintained the gelating ability of the compound, whilst Zn2+ and Ni2+ ions destroyed the gel. In addition, the introduction of Cu2+ ions caused the nanofiber gel to perform a chiral twist, whilst the Mg2+ ions enhanced the fluorescence of the gel. More interestingly, the Mg2+‐ion‐mediated organogel showed differences in the fluorescence quenching by D‐ and L‐tartaric acid, thus showing a chiral recognition ability.
Study of the Contributions of Non‐Specific and Specific Interactions during Fluoxetine Adsorption onto Activated Carbons
Authors: Román Silvia , Nabais João Manuel Valente , González Juan Félix , González‐García Carmen María , Ortiz Angel Luis
Published: March 2012

The adsorption of fluoxetine onto activated carbons (ACs) prepared from almond tree pruning by steam and CO2 activation under different temperature conditions (650–950°C), was studied. In both series increasing the temperature caused an increase in the BET apparent surface area, yielding ACs with SBET up to 870 and 710 m2 g−1 after steam and CO2 activation, respectively. Also, a slight widening of the porosity was found in both cases. In order to modify the functionality of the ACs, two of them were impregnated with triethylenediamine (TEDA) prior to the adsorption process, which caused a decrease in the AC apparent surface mainly due to micropore blockage. The fluoxetine adsorption isotherms at 25°C showed maximum adsorption capacities between 110 and 224 mg g−1. The adsorption isotherms were analyzed using Langmuir and Freundlich models. Although the impregnation reduced the pore volume, it did not cause a decrease in the fluoxetine maximum adsorption capacity, but a modification in the adsorption mechanism was observed.
Kinetics, Mechanistic and Thermodynamics of Zn(II) Ion Sorption: A Modeling Approach
Authors: Mishra Vishal , Balomajumder Chandrajit , Agarwal Vijay Kumar
Published: March 2012

Biosorption potential of Cedrus deodara sawdust (CDS) in terms of sorption of Zn(II) ion across liquid phase has been evaluated in the present investigation. The surface of the CDS biomass before the sorption of Zn(II) ions seemed to be more porous, non‐crystalline and heterogeneous. The maximum uptake capacity of CDS was 97.39 mg g−1. Sorption of Zn(II) ion on the surface of CDS sawdust was maximum at pH 5, temperature 45°C, initial concentration of Zn(II) ion 100 mg L−1, biomass dose 1 g L−1, contact time 150 min, and agitation rate 160 rpm. Pseudo second‐order kinetics with the highest linear regression coefficient (R2 = 0.99), and lowest values of error functions, i.e., chi (χ2) and sum of square errors (SSE) against pseudo first‐order rate kinetics showed that the sorption of Zn(II) ion on the surface of CDS was mediated by chemosoprtive forces of attraction rather than physical adsorption. Mechanistically, relatively higher proportion of sorption of Zn(II) ion in early phase of contact time was profoundly explained by Bangham's equation and film diffusivity (Df). Intraparticle or pore diffusion (Dp) of Zn(II) ion inside the pores of CDS was rate limiting step at the later stage of contact time. Furthermore, the thermodynamic study on sorption of metal ion delineated the fact that the Zn(II) sorption on the surface of CDS was spontaneous, endothermic together with increased entropy at solid liquid interface.
Structure‐Based Design of Novel Pyrimido[4,5‐c]pyridazine Derivatives as Dihydropteroate Synthase Inhibitors with Increased Affinity
Authors: Zhao Ying , Hammoudeh Dalia , Yun Mi‐Kyung , Qi Jianjun , White Stephen W. , Lee Richard E.
Published: March 2012

Dihydropteroate synthase (DHPS) is the validated drug target for sulfonamide antimicrobial therapy. However, due to widespread drug resistance and poor tolerance, the use of sulfonamide antibiotics is now limited. The pterin binding pocket in DHPS is highly conserved and is distinct from the sulfonamide binding site. It therefore represents an attractive alternative target for the design of novel antibacterial agents. We previously carried out the structural characterization of a known pyridazine inhibitor in the Bacillus anthracis DHPS pterin site and identified a number of unfavorable interactions that appear to compromise binding. With this structural information, a series of 4,5‐dioxo‐1,4,5,6‐tetrahydropyrimido[4,5‐c]pyridazines were designed to improve binding affinity. Most importantly, the N‐methyl ring substitution was removed to improve binding within the pterin pocket, and the length of the side chain carboxylic acid was optimized to fully engage the pyrophosphate binding site. These inhibitors were synthesized and evaluated by an enzyme activity assay, X‐ray crystallography, isothermal calorimetry, and surface plasmon resonance to obtain a comprehensive understanding of the binding interactions from structural, kinetic, and thermodynamic perspectives. This study clearly demonstrates that compounds lacking the N‐methyl substitution exhibit increased inhibition of DHPS, but the beneficial effects of optimizing the side chain length are less apparent.
Cell quantification: evolution of compartmentalization and distribution of iron‐oxide particles and labeled cells
Authors: Kotek Gyula , van Tiel Sandra T. , Wielopolski Piotr A. , Houston Gavin C. , Krestin Gabriel P. , Bernsen Monique R.
Published: March 2012

The purpose of the study was to show the feasibility of quantification in the case of cell death, cell migration and cell division by parametric MRI. We identify limitations for quantitative cell tracking owing to mixed parallel processes. Various intravoxel SPIO‐labeled cell, super paramagnetic iron oxide particles (SPIO) and micron‐sized paramagnetic iron oxide (MPIO) particle distributions were prepared by methods mimicking biologically relevant processes (compartmentalization, migration, division and cell death). R2* and R2 relaxometry measurements were performed at 3.0 T; iron concentration was measured by optical emission spectrometry. The effects of spatial distribution and compartmentalization of paramagnetic iron‐oxide particles on relaxivity were analyzed. Assessment of R2′ (R2*‐R2) allowed differentiation between intracellular and extracellular SPIO only if no high‐iron‐content extracellular particles were present. Relaxivity was sensitive to variations in cell labeling. Samples of the same cell types embedded in the same suspension media at the same cell density produced different relaxivity values, depending on the preparation of the labeled cells. In the case of cell division, a unique relationship between relaxation rate and iron concentration was found, where the relaxivity proved to be independent of initial cell labeling. In case of cell mixing, the cell density could be derived from relaxation values, even if iron concentration was undetermined. We demonstrated that relaxometry does not allow labeled cell quantification when multiple physiological processes such as cell division and cell migration coexist. The measured transversal relaxation rates were sensitive to the labeling technique. However, under special circumstances, despite the numerous limiting factors, quantification of the number of labeled cells by relaxometry was feasible. Copyright © 2012 John Wiley & Sons, Ltd.
Clinical implication of an insufficient number of examined lymph nodes after curative resection for gastric cancer
Authors: Son Taeil , Hyung Woo Jin , Lee Joong Ho , Kim Yoo Min , Kim Hyoung‐Il , An Ji Yeong , Cheong Jae‐Ho , Noh Sung Hoon
Published: March 2012

BACKGROUND:

The seventh edition of the tumor, lymph node (LN), metastasis (TNM) staging system increased the required number of examined LNs in gastric cancer from 15 to 16. However, the same staging system defines lymph node‐negative gastric cancer regardless of the number of examined LNs. In this study, the authors evaluated whether gastric cancer can be staged properly with fewer than 15 examined LNs.

METHODS:

The survival rates of 10,010 patients who underwent curative gastrectomy from 1987 to 2007 were analyzed. The patients were divided into 2 groups according to the number of examined LNs, termed the “insufficient” group (≤15 examined LNs) and the “sufficient” group (≥16 examined LNs). The survival curves of patients from both groups were compared according to the seventh edition of the TNM classification.

RESULTS:

Three hundred sixteen patients (3.2%) had ≤15 examined LNs for staging after they underwent standard, curative lymphadenectomy. Patients who had T1 tumor classification, N0 lymph node status, and stage I disease with an insufficient number of examined LNs after curative gastrectomy had a significantly worse prognosis than patients who had ≥16 examined LNs. Moreover, having an insufficient number of examined LNs was an independent prognostic factor for patients who had T1, N0, and stage I disease.

CONCLUSIONS:

Lymph node‐negative cancers in which ≤15 LNs were examined, classified as N0 in the new TNM staging system, could not adequately predict patient survival after curative gastrectomy, especially in patients with early stage gastric cancer. Cancer 2012. © 2012 American Cancer Society.
Effect of race and socioeconomic status on surgical margins and biochemical outcomes in an equal‐access health care setting
Authors: Chu David I. , Moreira Daniel M. , Gerber Leah , Presti Joseph C. , Aronson William J. , Terris Martha K. , Kane Christopher J. , Amling Christopher L. , Freedland Stephen J.
Published: March 2012

BACKGROUND:

The impact of race and socioeconomic status (SES) in prostate cancer (CaP) outcomes has been well‐studied, but controversy remains. The associations of race/SES with intermediate CaP outcomes, including positive surgical margin (PSM) and biochemical recurrence (BCR), were explored in an equal‐access setting.

METHODS:

Data were retrospectively collected from 2502 men in the Shared Equal Access Regional Cancer Hospitals (SEARCH) database who underwent radical prostatectomy from 1989 to 2010. SES (income, education, employment, and poverty) was estimated from linkage of home ZIP code to census data. Logistic regression with adjustment for pre‐ and postoperative covariates estimated risk for associations between race/SES and pathologic outcomes. Cox proportional hazards models estimated risk for associations between race/SES and time to BCR.

RESULTS:

Black men were more likely to have lower SES than white men (P < .001). On multivariate analysis, race was not associated with PSM, but higher SES was associated with less PSM and fewer Gleason sum ≥ 7 pathologic tumors when SES was assessed by education, employment, or poverty (P trend ≤ .051) and income, employment, or poverty (P trend ≤ 0.059), respectively. Crude Cox models showed black men had higher BCR risk (hazards ratio = 1.20, 95% confidence interval = 1.05‐1.38, P = .009) that persisted after adjustment for covariates including SES (hazards ratio ≥ 1.18, P ≤ .040). Higher SES measured by income and poverty were associated with less BCR, but only for black men (P trend ≤ .048).

CONCLUSIONS:

Even in an equal‐access setting, higher SES predicted lower PSM risk, and race persisted in predicting BCR despite adjustment for SES. Low SES black patients may be at greatest risk for postprostatectomy BCR. Cancer 2012. © 2012 American Cancer Society.
Costs and trends in pancreatic cancer treatment
Authors: O'Neill Caitriona B. , Atoria Coral L. , O'Reilly Eileen M. , LaFemina Jennifer , Henman Martin C. , Elkin Elena B.
Published: March 2012

BACKGROUND:

Pancreatic cancer poses a substantial morbidity and mortality burden in the United States, and predominantly affects older adults. The objective of this study was to estimate the direct medical costs of pancreatic cancer treatment in a population‐based cohort of Medicare beneficiaries, and the contribution of different treatment modalities and health care services to the total cost of care and trends in costs over time.

METHODS:

In the linked Surveillance, Epidemiology, and End Results (SEER)‐Medicare database, pancreatic cancer patients were identified who were aged 66 years or older and who were diagnosed from 2000 to 2007. Total direct medical costs were estimated from Medicare payments overall and within categories of care. Costs attributable to pancreatic cancer were estimated by subtracting the costs of medical care in a matched cohort of cancer‐free beneficiaries.

RESULTS:

A total of 15,037 patients were identified, of whom 97% were observed from diagnosis until death. Mean total direct medical costs were $65,500. Mean total costs were greater for patients with resectable locoregional disease ($134,700) than for those with unresectable locoregional or distant disease ($65,300 and $49,000, respectively). Hospitalizations and cancer‐directed procedures collectively accounted for the largest fraction of health care costs. The total cost of care appeared to increase slightly over the study period (P = .05). The mean costs attributable to pancreatic cancer were $61,700.

CONCLUSIONS:

Despite poor prognosis and short survival, the economic burden of pancreatic cancer in the elderly is substantial. Demographic trends, greater use of targeted therapies, and possible implementation of screening strategies are likely to impact treatment patterns and costs in the future. Cancer 2012. © 2012 American Cancer Society.
Late effects of chemotherapy and radiotherapy in osteosarcoma and Ewing sarcoma patients
Authors: Longhi Alessandra , Ferrari Stefano , Tamburini Angela , Luksch Roberto , Fagioli Franca , Bacci Gaetano , Ferrari Cristina
Published: March 2012

BACKGROUND:

Patients with osteosarcoma and Ewing sarcoma have achieved longer survival over the past decades, but late side effects of chemotherapy and radiotherapy have become important concerns.

METHODS:

The authors reviewed all patients with localized osteosarcoma or Ewing sarcoma who had been enrolled in the Italian Sarcoma Group neoadjuvant protocols from 1983 through 2006. Data were updated in December 2010 to determine 3 endpoints: the incidence of a secondary primary cancer (designated as “second malignant neoplasm” [SMN]), infertility, and cardiotoxicity.

RESULTS:

Data were available on 883 patients with osteosarcoma and 543 patients with Ewing sarcoma. In the osteosarcoma group, there were 39 SMNs (4.4%) in 36 patients; in the Ewing sarcoma group, 15 patients (2.8%) experienced a single SMN each. The cumulative 10‐year and 20‐year incidence of an SMN (±standard error) was 4.9% ± 0.9% and 6.1% ± 1.2%, respectively, in the osteosarcoma group and 3.4% ± 0.9% and 4.7% ± 1.6%, respectively, in the Ewing sarcoma group. The most common SMN in the osteosarcoma group was breast cancer (n = 11), and the most common SMN in the Ewing sarcoma group was radiotherapy‐induced osteosarcoma (n = 6). After 20 years, the risk of developing an SMN increased, whereas the risk of a recurrence of the primary tumor decreased. Permanent sterility was more common in males than in females. Doxorubicin cardiotoxicity occurred in 18 patients with osteosarcoma (2%) and in 7 patients with Ewing sarcoma (1.3%).

CONCLUSIONS:

The awareness of late side effects in long‐term survivors of primary bone cancers should encourage longer follow‐up. Cancer 2012. © 2012 American Cancer Society.