bluuebunny/crossref_metadata_2025_split huggingface dataset:
Middle Paleolithic human remains from the Gruta Da Oliveira (Torres Novas), Portugal
Authors: Willman John C. , Maki Julia , Bayle Priscilla , Trinkaus Erik , Zilhão João 
Published: May 2012

AbstractAdditional Middle Paleolithic human remains from layers 17, 18, and 22 of the Gruta da Oliveira, Portugal consist of a proximal manual phalanx 2 (Oliveira 5), a partial postcanine tooth (Oliveira 6), a humeral diaphysis (Oliveira 7), a distal mandibular molar (Oliveira 8), and a mandibular premolar (P3) (Oliveira 9). Oliveira 5, 6, and 8 are unremarkable for Late Pleistocene humans. The Oliveira 7 right humerus is moderately robust or the individual had the stocky body proportions of other European (including Iberian) Neandertals. The Oliveira 9 P3 has a large and symmetrical crown and lacks a distal accessory ridge and accessory lingual cusps, overlapping both Neandertal and recent human ranges of variation. It contrasts with at least recent human P3s in having relatively thin enamel. These join the Oliveira 1 to 4 remains in further documenting early MIS 3 Neandertal morphology in western Iberia. Am J Phys Anthropol 2012. © 2012 Wiley Periodicals, Inc.
Application of microwave‐assisted click chemistry in the preparation of functionalized copolymers for drug conjugation
Authors: Hu Xiuli , Yan Lesan , Xiao Haihua , Li Xiaoyuan , Jing Xiabin 
Published: May 2012

AbstractThe aim of this study is to develop azido‐carrying biodegradable polymers and their postfunctionalization with alkynyl compounds via click chemistry and to investigate their potential use in drug delivery. Azido polymers were prepared by ring‐opening polymerization of cyclic carbonate monomer, 2,2‐bis(azidomethyl)trimethylene carbonate (ATC) with lactide using stannous octoate as catalyst. Several alkynyl compounds were selected to investigate the feasibility and reaction condition of click chemistry. With microwave‐assisting, the reaction time of click chemistry was shortened to 5 min. By using poly(ethylene glycol) (PEG) as macroinitiator, amphiphilic block copolymer mPEG‐b‐P(LA‐co‐ATC) was obtained and it could self‐assemble into micelles by solvent replacement method. The pendant groups were used for conjugating anticancer drugs gemcitabine and paclitaxel and fluorescent dye Rhodamine B. 3‐(4,5‐Dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide was used to assay the cytotoxicity of the conjugate micelles against SKOV‐3 and HeLa cell lines. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013
The interferon signature and STAT1 expression in rheumatoid arthritis synovial fluid macrophages are induced by tumor necrosis factor α and counter‐regulated by the synovial fluid microenvironment
Authors: Gordon Rachael A. , Grigoriev Galina , Lee Angela , Kalliolias George D. , Ivashkiv Lionel B. 
Published: May 2012

AbstractObjectiveType I interferons (IFNs) have emerged as potential activators of the IFN signature and elevated STAT‐1 expression in rheumatoid arthritis (RA) synovium, but mechanisms that induce synovial IFN expression are unknown. Recently, tumor necrosis factor α (TNFα) was shown to induce a delayed IFN response in macrophages. We undertook this study to test whether TNFα, classically thought to activate inflammatory NF‐κB target genes in RA, also contributes to the “IFN signature” in RA synovial macrophages.MethodsSynovial fluid (SF) macrophages purified from 24 patients with RA and 18 patients with spondylarthritides (SpA) were lysed immediately after isolation or were cultured ex vivo in the absence or presence of blockade of endogenous type I IFN or TNFα. Expression of IFN‐inducible target genes was measured by quantitative reverse transcription–polymerase chain reaction, and expression of their corresponding proteins was measured by enzyme‐linked immunosorbent assay.ResultsExpression of an IFN signature and STAT1 in RA synovial macrophages was suppressed when type I IFNs or TNFα were blocked, whereas TNFα blockade did not affect expression of IFN response genes or STAT1 in SpA synovial macrophages. RA SF suppressed the IFN signature in RA synovial macrophages and in TNFα‐, IFNα‐, and IFNβ‐stimulated control macrophages. Type I IFNs suppressed expression of IL8 and MMP9 in RA synovial macrophages and in TNFα‐stimulated control macrophages.ConclusionOur findings identify a new function of TNFα in RA synovitis by implicating TNFα as a major inducer of the RA synovial IFN response. The results suggest that the expression of IFN response genes in RA synovium is regulated by interplay between TNFα and opposing homeostatic factors expressed in the synovial microenvironment.
Organic–Inorganic Hybrids Based on Ultrathin Oxide Layers: Designed Nanostructures for Molecular Recognition
Authors: Okada Tomohiko , Ide Yusuke , Ogawa Makoto 
Published: May 2012

AbstractThe application of layered solids for molecular recognition is summarized. By using layered solids (silicates, aluminosilicates, titanates, hydroxides, and so on), ions and molecules can be concentrated from aqueous and vapor phases. The large surface area and tunable surface properties derived from the layered structures contribute to molecular recognition. The choice of materials and modification of the nanostructure were carefully investigated to optimize the performance based on molecular recognition (selective adsorption, substrate selective reaction, detection, etc.). The progress made in materials syntheses (variation of layered materials, sophisticated modification, controlled morphology, and processing) has made the design of materials more attractive and realistic.
Integrated biogas upgrading and hydrogen utilization in an anaerobic reactor containing enriched hydrogenotrophic methanogenic culture
Authors: Luo Gang , Angelidaki Irini 
Published: May 2012

AbstractBiogas produced by anaerobic digestion, is mainly used in a gas motor for heat and electricity production. However, after removal of CO2, biogas can be upgraded to natural gas quality, giving more utilization possibilities, such as utilization as autogas, or distant utilization by using the existing natural gas grid. The current study presents a new biological method for biogas upgrading in a separate biogas reactor, containing enriched hydrogenotrophic methanogens and fed with biogas and hydrogen. Both mesophilic‐ and thermophilic anaerobic cultures were enriched to convert CO2 to CH4 by addition of H2. Enrichment at thermophilic temperature (55°C) resulted in CO2 and H2 bioconversion rate of 320 mL CH4/(gVSS h), which was more than 60% higher than that under mesophilic temperature (37°C). Different dominant species were found at mesophilic‐ and thermophilic‐enriched cultures, as revealed by PCR–DGGE. Nonetheless, they all belonged to the order Methanobacteriales, which can mediate hydrogenotrophic methanogenesis. Biogas upgrading was then tested in a thermophilic anaerobic reactor under various operation conditions. By continuous addition of hydrogen in the biogas reactor, high degree of biogas upgrading was achieved. The produced biogas had a CH4 content, around 95% at steady‐state, at gas (mixture of biogas and hydrogen) injection rate of 6 L/(L day). The increase of gas injection rate to 12 L/(L day) resulted in the decrease of CH4 content to around 90%. Further study showed that by decreasing the gas–liquid mass transfer by increasing the stirring speed of the mixture the CH4 content was increased to around 95%. Finally, the CH4 content around 90% was achieved in this study with the gas injection rate as high as 24 L/(L day). Biotechnol. Bioeng. 2012; 109: 2729–2736. © 2012 Wiley Periodicals, Inc.
AS1411 aptamer tagged PLGA‐lecithin‐PEG nanoparticles for tumor cell targeting and drug delivery
Authors: Aravind Athulya , Jeyamohan Prashanti , Nair Remya , Veeranarayanan Srivani , Nagaoka Yutaka , Yoshida Yasuhiko , Maekawa Toru , Kumar D. Sakthi 
Published: May 2012

AbstractLiposomes and polymers are widely used drug carriers for controlled release since they offer many advantages like increased treatment effectiveness, reduced toxicity and are of biodegradable nature. In this work, anticancer drug‐loaded PLGA‐lecithin‐PEG nanoparticles (NPs) were synthesized and were functionalized with AS1411 anti‐nucleolin aptamers for site‐specific targeting against tumor cells which over expresses nucleolin receptors. The particles were characterized by transmission electron microscope (TEM) and X‐ray photoelectron spectroscopy (XPS). The drug‐loading efficiency, encapsulation efficiency and in vitro drug release studies were conducted using UV spectroscopy. Cytotoxicity studies were carried out in two different cancer cell lines, MCF‐7 and GI‐1 cells and two different normal cells, L929 cells and HMEC cells. Confocal microscopy and flowcytometry confirmed the cellular uptake of particles and targeted drug delivery. The morphology analysis of the NPs proved that the particles were smooth and spherical in shape with a size ranging from 60 to 110 nm. Drug‐loading studies indicated that under the same drug loading, the aptamer‐targeted NPs show enhanced cancer killing effect compared to the corresponding non‐targeted NPs. In addition, the PLGA‐lecithin‐PEG NPs exhibited high encapsulation efficiency and superior sustained drug release than the drug loaded in plain PLGA NPs. The results confirmed that AS1411 aptamer‐PLGA‐lecithin‐PEG NPs are potential carrier candidates for differential targeted drug delivery. Biotechnol. Bioeng. 2012; 109: 2920–2931. © 2012 Wiley Periodicals, Inc.
Enhancement of neutral lipid productivity in the microalga Isochrysis affinis Galbana (T‐Iso) by a mutation‐selection procedure
Authors: Bougaran Gaël , Rouxel Catherine , Dubois Nolwenn , Kaas Raymond , Grouas Sophie , Lukomska Ewa , Le Coz Jean‐René , Cadoret Jean‐Paul 
Published: May 2012

AbstractMicroalgae offer a high potential for energetic lipid storage as well as high growth rates. They are therefore considered promising candidates for biofuel production, with the selection of high lipid‐producing strains a major objective in projects on the development of this technology. We developed a mutation‐selection method aimed at increasing microalgae neutral lipid productivity. A two step method, based on UVc irradiation followed by flow cytometry selection, was applied to a set of strains that had an initial high lipid content and improvement was assessed by means of Nile‐red fluorescence measurements. The method was first tested on Isochrysis affinis galbana (T‐Iso). Following a first round of mutation‐selection, the total fatty acid content had not increased significantly, being $262\pm 21\,{\rm mgTFA}\,{\rm (gC)}^{- {\rm 1}} $ for the wild type (WT) and $269\pm 49\,{\rm mgTFA}\,{\rm (gC)}^{- {\rm 1}} $ for the selected population (S1M1). Conversely, fatty acid distribution among the lipid classes was affected by the process, resulting in a 20% increase for the fatty acids in the neutral lipids and a 40% decrease in the phospholipids. After a second mutation‐selection step (S2M2), the total fatty acid content reached $409\pm 64\,{\rm mgTFA}\,{\rm (gC)}^{- {\rm 1}} $ with a fatty acid distribution similar to the S1M1 population. Growth rate remained unaffected by the process, resulting in a 80% increase for neutral lipid productivity. Biotechnol. Bioeng. 2012; 109: 2737–2745. © 2012 Wiley Periodicals, Inc.
Biodefluorination and biotransformation of fluorotelomer alcohols by two alkane‐degrading Pseudomonas strains
Authors: Kim Myung Hee , Wang Ning , McDonald Thomas , Chu Kung‐Hui 
Published: May 2012

AbstractFluorotelomer alcohols [FTOHs, F(CF2)nCH2CH2OH, n = 4, 6, and 8] are emerging environmental contaminants. Biotransformation of FTOHs by mixed bacterial cultures has been reported; however, little is known about the microorganisms responsible for the biotransformation. Here we reported biotransformation of FTOHs by two well‐studied Pseudomonas strains: Pseudomonas butanovora (butane oxidizer) and Pseudomonas oleovorans (octane oxidizer). Both strains could defluorinate 4:2, 6:2, and 8:2 FTOHs, with a higher degree of defluorination for 4:2 FTOH. According to the identified metabolites, P. oleovorans transformed FTOHs via two pathways I and II. The pathway I led to the production of x:2 ketone [dominant metabolite, F(CF2)xC(O)CH3; x = n − 1, n = 6 or 8], x:2 sFTOH [F(CF2)xCH(OH)CH3], and perfluorinated carboxylic acids (PFCAs, perfluorohexanoic, or perfluorooctanoic acid). The pathway II resulted in the formation of x:3 polyfluorinated acid [F(CF2)xCH2CH2COOH] and relatively minor shorter‐chain PFCAs (perfluorobutyric or perfluorohexanoic acid). Conversely, P. butanovora transformed FTOHs by using the pathway I, leading to the production of x:2 ketone, x:2 sFTOH, and PFCAs. This is the first study to show that individual bacterium can bio‐transform FTOHs via different or preferred transformation pathways to remove multiple CF2 groups from FTOHs to form shorter‐chain PFCAs. Biotechnol. Bioeng. 2012; 109: 3041–3048. © 2012 Wiley Periodicals, Inc.
Papain‐Specific Activating Esters in Aqueous Dipeptide Synthesis
Authors: de Beer Roseri J. A. C. , Zarzycka Barbara , Mariman Michiel , Amatdjais‐Groenen Helene I. V. , Mulders Marc J. , Quaedflieg Peter J. L. M. , van Delft Floris L. , Nabuurs Sander B. , Rutjes Floris P. J. T. 
Published: May 2012

AbstractEnzymatic peptide synthesis has the potential to be a viable alternative for chemical peptide synthesis. Because of the increasing commercial interest in peptides, new and improved enzymatic synthesis methods are desirable. In recently developed enzymatic strategies such as substrate mimetic approaches and enzyme‐specific activation, use of the guanidinophenyl ester (OGp) group has been shown to suffer from some drawbacks. OGp esters are sensitive to spontaneous chemical hydrolysis and the group is expensive to synthesize and therefore not suitable for large‐scale applications. On the basis of earlier computational studies, we hypothesized that OGp might be replaceable by simpler ester groups to make the enzyme‐specific activation approach to peptide bond formation more accessible. To this end, a set of potential activating esters (Z‐Gly‐Act) was designed, synthesized, and evaluated. Both the benzyl (OBn) and the dimethylaminophenyl (ODmap) esters gave promising results. For these esters, the scope of a model dipeptide synthesis reaction under aqueous conditions was investigated by varying the amino acid donor. The results were compared with those obtained from a previous study of Z‐XAA‐OGp esters. Computational docking analysis of the set of esters was performed in order to provide insight into the differences in the reactivities of all the potential activating esters. Finally, selected ODmap‐ and OBn‐activated amino acids were applied in the synthesis of two biologically active dipeptides on preparative scales.
Recognition by Nonaromatic and Stereochemical Subunit‐Containing Polyamides of the Four Watson–Crick Base Pairs in the DNA Minor Groove
Authors: Zhang Hong‐Fei , Wu Yan‐Ling , Jiang Shi‐Kun , Wang Pu , Sugiyama Hiroshi , Chen Xing‐Lai , Zhang Wen , Ji Yan‐Juan , Guo Chuan‐Xin 
Published: May 2012

AbstractIn order to develop an optimal subunit as a T‐recognition element in hairpin polyamides, 15 novel chirality‐modified polyamides containing (R)‐α,β‐diaminopropionic acid (Rβ), (S)‐α,β‐diaminopropionic acid (Sβ), (1R,3S)‐3‐aminocyclopentanecarboxylic acid (RSCp), (1S,3R)‐3‐amino‐cyclopentanecarboxylic acid (RSCp), (1R,3R)‐3‐aminocyclopentanecarboxylic acid (RRCp) and (1S,3S)‐3‐amino‐cyclopentanecarboxylic acid (SSCp) residues were synthesized. Their binding characteristics to DNA sequences 5′‐TGCNCAT‐3′/3′‐ACGN′GTA‐5′ (N⋅N′=A⋅T, T⋅A, G⋅C and C⋅G) were systemically studied by surface plasmon resonance (SPR) and molecular simulation (MSim) techniques. SPR showed that polyamide 4, AcIm‐Sβ‐ImPy‐γ‐ImPy‐β‐Py‐βDp (β/Sβ pair), bound to a DNA sequence containing a core binding site of 5′‐TGCACAT‐3′ with a dissociation equilibrium constant (KD) of 4.5×10−8 m. This was a tenfold improvement in specificity over 5′‐TGCTCAT‐3′ (KD=4.5×10−7 M). MSim studies supported the SPR results. More importantly, for the first time, we found that chiral 3‐aminocyclopentanecarboxylic acids in polyamides can be employed as base readers with only a small decrease in binding affinity to DNA. In particular, SPR showed that polyamide 9 (RRCp/β pair) had a 15‐fold binding preference for 5′‐TGCTCAT‐3′ over 5′‐TGCACAT‐3′. A large difference in standard free energy change for A⋅T over T⋅A was determined (ΔΔGo=5.9 kJ mol−1), as was a twofold decrease in interaction energy by MSim. Moreover, a 1:1 stoichiometry (9 to 5′‐TGCTCAT‐3′/3′‐ACGAGTA‐5′) was shown by MSim to be optimal for the chiral five‐membered cycle to fit the minor groove. Collectively, the study suggests that the (S)‐α‐amino‐β‐aminopropionic acid and (1R,3R)‐3‐aminocyclopentanecarboxylic acid can serve as a T‐recognition element, and the stereochemistry and the nature of these subunits significantly influence binding properties in these recognition events. Subunit (1R,3R)‐3‐aminocyclopentanecarboxylic acid broadens our scope to design novel polyamides.
Iatrogenic pulmonary artery rupture during Swan–Ganz catheter placement—A novel therapeutic approach
Authors: Kalra Ankur , Heitner Stephen , Topalian Simon 
Published: May 2012

AbstractPulmonary artery rupture (PAR) is a rare but deadly complication (incidence of 0.03–0.2% of all PA cannulations), with mortality in the region of 70%. We report a case of an 88‐year‐old woman with iatrogenic PAR as a result of Swan–Ganz catheter placement. A rapid successful isolation and occlusion of the culprit PA branch via the deployment of an Amplatzer® Vascular Plug (AGA Medical Corporation, North Plymouth, MN) was performed. To our knowledge, this is the first case report where this device has been used as therapy in PAR. © 2012 Wiley Periodicals, Inc.
Constructing Organic D–A–π‐A‐Featured Sensitizers with a Quinoxaline Unit for High‐Efficiency Solar Cells: The Effect of an Auxiliary Acceptor on the Absorption and the Energy Level Alignment
Authors: Pei Kai , Wu Yongzhen , Wu Wenjun , Zhang Qiong , Chen Baoqin , Tian He , Zhu Weihong 
Published: May 2012

AbstractFour organic D–A–π‐A‐featured sensitizers (TQ1, TQ2, IQ1, and IQ2) have been studied for high‐efficiency dye‐sensitized solar cells (DSSCs). We employed an indoline or a triphenylamine unit as the donor, cyanoacetic acid as the acceptor/anchor, and a thiophene moiety as the conjugation bridge. Additionally, an electron‐withdrawing quinoxaline unit was incorporated between the donor and the π‐conjugation unit. These sensitizers show an additional absorption band covering the broad visible range in solution. The contribution from the incorporated quinoxaline was investigated theoretically by using DFT and time‐dependent DFT. The incorporated low‐band‐gap quinoxaline unit as an auxiliary acceptor has several merits, such as decreasing the band gap, optimizing the energy levels, and realizing a facile structural modification on several positions in the quinoxaline unit. As demonstrated, the observed additional absorption band is favorable to the photon‐to‐electron conversion because it corresponds to the efficient electron transitions to the LUMO orbital. Electrochemical impedance spectroscopy (EIS) Bode plots reveal that the replacement of a methoxy group with an octyloxy group can increase the injection electron lifetime by a factor of 2.4. IQ2 and TQ2 can perform well without any co‐adsorbent, successfully suppress the charge recombination from TiO2 conduction band to I3− in the electrolyte, and enhance the electron lifetime, resulting in a decreased dark current and enhanced open circuit voltage (Voc) values. By using a liquid electrolyte, DSSCs based on dye IQ2 exhibited a broad incident photon‐to‐current conversion efficiency (IPCE) action spectrum and high efficiency (η=8.50 %) with a short circuit current density (Jsc) of 15.65 mA cm−2, a Voc value of 776 mV, a fill factor (FF) of 0.70 under AM 1.5 illumination (100 mW cm−2). Moreover, the overall efficiency remained at 97 % of the initial value after 1000 h of visible‐light soaking.
Definition of an Intramolecular Eu‐to‐Eu Energy Transfer within a Discrete [Eu2L] Complex in Solution
Authors: Nonat Aline , Regueiro‐Figueroa Martín , Esteban‐Gómez David , de Blas Andrés , Rodríguez‐Blas Teresa , Platas‐Iglesias Carlos , Charbonnière Loïc J. 
Published: May 2012

AbstractLigand L, based on two do3a moieties linked by the methylene groups of 6,6′‐dimethyl‐2,2′‐bipyridine, was synthesized and characterized. The addition of Ln salts to an aqueous solution of L (0.01 M Tris‐HCl, pH 7.4) led to the successive formation of [LnL] and [Ln2L] complexes, as evidenced by UV/Vis and fluorescence titration experiments. Homodinuclear [Ln2L] complexes (Ln=Eu, Gd, Tb, Yb, and Lu) were prepared and characterized. The 1H and 13C NMR spectra of the Lu and Yb complexes in D2O solution (pD=7.0) showed C1 symmetry of these species in solution, pointing to two different chemical environments for the two lanthanide cations. The analysis of the chemical shifts of the Yb complex indicated that the two coordination sites present square antiprismatic (SAP) coordination environments around the metal ions. The spectroscopic properties of the [Tb2L] complex upon ligand excitation revealed conventional behavior with τH2O=2.05(1) ms and ϕH2O=51 %, except for the calculation of the hydration number obtained from the luminescent lifetimes in H2O and D2O, which pointed to a non‐integer value of 0.6 water molecules per TbIII ion. In contrast, the Eu complex revealed surprising features such as: 1) the presence of two and up to five components in the 5D0→7F0 and 5D0→7F1 emission bands, respectively; 2) marked differences between the normalized spectra obtained in H2O and D2O solutions; and 3) unconventional temporal evolution of the luminescence intensity at certain wavelengths, the intensity profile first displaying a rising step before the occurrence of the expected decay. Additional spectroscopic experiments performed on [Gd2−xEuxL] complexes (x=0.1 and 1.9) confirmed the presence of two distinct Eu sites with hydration numbers of 0 (site I) and 2 (site II), and showed that the unconventional temporal evolution of the emission intensity is the result of an unprecedented intramolecular Eu‐to‐Eu energy‐transfer process. A mathematical model was developed to interpret the experimental data, leading to energy‐transfer rates of 0.98 ms−1 for the transfer from the site with q=0 to that with q=2 and vice versa. Hartree–Fock (HF) and density functional theory (DFT) calculations performed at the B3LYP level were used to investigate the conformation of the complex in solution, and to estimate the intermetallic distance, which provided Förster radii (R0) values of 8.1 Å for the energy transfer from site I to site II, and 6.8 Å for the reverse energy transfer. These results represent the first evidence of an intramolecular energy‐transfer equilibrium between two identical lanthanide cations within a discrete molecular complex in solution.
DOTAGA–Anhydride: A Valuable Building Block for the Preparation of DOTA‐Like Chelating Agents
Authors: Bernhard Claire , Moreau Mathieu , Lhenry Damien , Goze Christine , Boschetti Frédéric , Rousselin Yoann , Brunotte François , Denat Franck 
Published: May 2012

AbstractA DOTA derivative that contains an anhydride group was readily synthesized by reacting DOTAGA with acetic anhydride and its reactivity was investigated. Opening the anhydride with propylamine led to the selective formation of one of two possible regioisomers. The structure of the obtained isomer was unambiguously determined by 1D and 2D NMR experiments, including COSY, HMBC, and NOESY techniques. This bifunctional chelating agent offers a convenient and attractive approach for labeling biomolecules and, more generally, for the synthesis of a large range of DOTA derivatives. The scope of the reaction was extended to prepare DOTA‐like compounds that contained various functional groups, such as isothiocyanate, thiol, ester, and amino acid moieties. This versatile building block was also used for the synthesis of a bimodal tag for SPECT or PET/optical imaging.