bluuebunny/crossref_metadata_2025 huggingface dataset:
Non-Culture Diagnostics for Invasive Candidiasis: Promise and Unintended Consequences
Authors: Clancy Cornelius , Nguyen M. Hong
Published: February 2018

Blood cultures are positive for Candida species in < 50% and < 20% of hematogenously disseminated and intra-abdominal candidiasis, respectively. Non-culture tests such as mannan, anti-mannan antibody, Candida albicans germ tube antibody (CAGTA), 1,3-β-d-glucan (BDG), the T2Candida nanodiagnostic panel, and polymerase chain reaction (PCR) are available for clinical use, but their roles in patient care are uncertain. Sensitivity/specificity of combined mannan/anti-mannan, BDG, T2Candida and PCR for candidemia are ~80%/80%, ~80%/80%, ~90%/98%, and ~90%/90%, respectively. Limited data for intra-abdominal candidiasis suggest CAGTA, BDG sensitivity/specificity of ~65%/75% and PCR sensitivity of ~85–90%. PCR specificity has varied widely for intra-abdominal candidiasis (33–97%), and T2Candida data are lacking. Tests will be useful if restricted to cases in which positive and negative predictive values (PPVs, NPVs) differ in a clinically meaningful way from the pre-test likelihood of invasive candidiasis. In some patients, PPVs are sufficient to justify antifungal treatment, even if blood cultures are negative. In most patients, NPVs of each test are excellent, which may support decisions to withhold antifungal therapy. If test results are not interpreted judiciously, non-culture diagnostics may have unintended consequences for stewardship and infection prevention programs. In particular, discrepant non-culture test-positive/culture-negative results may promote inappropriate antifungal treatment of patients who are unlikely to have candidiasis, and lead to spurious reporting of hospital-acquired infections. In conclusion, non-culture Candida diagnostics have potential to advance patient care, but this promise will be realized only if users understand tests’ strengths and limitations, and plan proactively for how best to employ them at their hospitals.
Gene Environment Interactions and Predictors of Colorectal Cancer in Family-Based, Multi-Ethnic Groups
Authors: Shiao S. Pamela K. , Grayson James , Yu Chong Ho , Wasek Brandi , Bottiglieri Teodoro
Published: February 2018

For the personalization of polygenic/omics-based health care, the purpose of this study was to examine the gene–environment interactions and predictors of colorectal cancer (CRC) by including five key genes in the one-carbon metabolism pathways. In this proof-of-concept study, we included a total of 54 families and 108 participants, 54 CRC cases and 54 matched family friends representing four major racial ethnic groups in southern California (White, Asian, Hispanics, and Black). We used three phases of data analytics, including exploratory, family-based analyses adjusting for the dependence within the family for sharing genetic heritage, the ensemble method, and generalized regression models for predictive modeling with a machine learning validation procedure to validate the results for enhanced prediction and reproducibility. The results revealed that despite the family members sharing genetic heritage, the CRC group had greater combined gene polymorphism rates than the family controls (p < 0.05), on MTHFR C677T, MTR A2756G, MTRR A66G, and DHFR 19 bp except MTHFR A1298C. Four racial groups presented different polymorphism rates for four genes (all p < 0.05) except MTHFR A1298C. Following the ensemble method, the most influential factors were identified, and the best predictive models were generated by using the generalized regression models, with Akaike’s information criterion and leave-one-out cross validation methods. Body mass index (BMI) and gender were consistent predictors of CRC for both models when individual genes versus total polymorphism counts were used, and alcohol use was interactive with BMI status. Body mass index status was also interactive with both gender and MTHFR C677T gene polymorphism, and the exposure to environmental pollutants was an additional predictor. These results point to the important roles of environmental and modifiable factors in relation to gene–environment interactions in the prevention of CRC.
Sensors and Actuators in Smart Cities
Authors: Hammoudeh Mohammad , Arioua Mounir
Published: February 2018

With the city, from its earliest emergence in the Near East between 4500 and 3100 BCE, came a wide range of new discoveries and inventions, from synthetic materials to wheeled vehicles[...]
Living on the Global Peripheries of Law: Disability Human Rights Law in Principle and in Practice in the Global South
Authors: Chouinard Vera
Published: February 2018

This article develops the notion that poorer nations of the Global South are particularly disadvantaged in terms of realizing disabled people's human rights in practice. This is because they are situated in what is termed the global peripheries of law. These are peripheries in which very limited human and financial resources are available to practically realize disability human rights (reflecting processes such as the outmigration of trained professionals, devaluation of currency as a condition of debt repayment, and dependence on agricultural exports and imports of expensive manufactured goods, including medicine, from the Global North). Being on the global peripheries of law also reflects legacies of colonial and neo-colonial violence and oppression in an unequal global capitalist order, such as ongoing and widespread violence against women and unsafe working conditions—both of which result in death and the geographically uneven production of impairment. This uneven production of impairment also needs to be considered as an important part of understanding disability human rights law in a global context. Following a brief overview of the U.N. convention on the human rights of disabled people and the U.N. Covenant on Economic, Social and Cultural Rights to provide a global legal context and of the Inter-American Human Rights System to provide a regional legal context, the article illustrates why it is so difficult to realize disabled people's human rights in practice in the Global South, through a case study of Guyana.
4,7-Dichloro[1,2,5]oxadiazolo[3,4-d]pyridazine 1-oxide
Authors: Chmovzh Timofey , Knyazeva Ekaterina , Popov Vadim , Rakitin Oleg
Published: February 2018

Dihalogenated derivatives of [1,2,5]chalcogenadiazolo[3,4-d]pyridazines are of interest as precursors for both photovoltaic materials and biologically active compounds. In this communication, 4,7-dichloro[1,2,5]oxadiazolo[3,4-d]pyridazine 1-oxide was prepared via the reaction of 3,6-dichloro-5-nitropyridazin-4-amine with oxidizing agents; the best yield of the target compound was achieved in the reaction with (diacetoxyiodo)benzene in benzene by heating at reflux for two hours. The structure of the newly synthesized compound was established by means of 13C-NMR and IR spectroscopy, mass-spectrometry and elemental analysis.
Dimethyl 2,2′-[Carbonylbis(azanediyl)](2S,2′S)-bis[3-(4-hydroxyphenyl)propanoate]
Authors: Mancuso Raffaella , Gioia Katia , Piccionello Antonio , Della Ca’ Nicola , Carfagna Carla , Gabriele Bartolo
Published: February 2018

The thus-far unknown ureic derivative dimethyl 2,2′-[carbonylbis(azanediyl)](2S,2′S)-bis[3-(4-hydroxyphenyl)propanoate] has been efficiently synthesized by enantiospecific oxidative carbonylation of readily available l-tyrosine methyl ester, using a very simple catalytic system (PdI2 in conjunction with KI) under relatively mild conditions (100 °C for 5 h in DME as the solvent and under 20 atm of a 4:1 mixture CO-air).
Analysis Method for Laterally Loaded Pile Groups Using an Advanced Modeling of Reinforced Concrete Sections
Authors: Stacul Stefano , Squeglia Nunziante
Published: February 2018

A Boundary Element Method (BEM) approach was developed for the analysis of pile groups. The proposed method includes: the non-linear behavior of the soil by a hyperbolic modulus reduction curve; the non-linear response of reinforced concrete pile sections, also taking into account the influence of tension stiffening; the influence of suction by increasing the stiffness of shallow portions of soil and modeled using the Modified Kovacs model; pile group shadowing effect, modeled using an approach similar to that proposed in the Strain Wedge Model for pile groups analyses. The proposed BEM method saves computational effort compared to more sophisticated codes such as VERSAT-P3D, PLAXIS 3D and FLAC-3D, and provides reliable results using input data from a standard site investigation. The reliability of this method was verified by comparing results from data from full scale and centrifuge tests on single piles and pile groups. A comparison is presented between measured and computed data on a laterally loaded fixed-head pile group composed by reinforced concrete bored piles. The results of the proposed method are shown to be in good agreement with those obtained in situ.
Highly Efficient Intracellular Protein Delivery by Cationic Polyethyleneimine-Modified Gelatin Nanoparticles
Authors: Chou Ming-Ju , Yu Hsing-Yi , Hsia Jui-Ching , Chen Ying-Hou , Hung Tzu-Ting , Chao Hsiao-Mei , Chern Edward , Huang Yi-You
Published: February 2018

Intracellular protein delivery may provide a safe and non-genome integrated strategy for targeting abnormal or specific cells for applications in cell reprogramming therapy. Thus, highly efficient intracellular functional protein delivery would be beneficial for protein drug discovery. In this study, we generated a cationic polyethyleneimine (PEI)-modified gelatin nanoparticle and evaluated its intracellular protein delivery ability in vitro and in vivo. The experimental results showed that the PEI-modified gelatin nanoparticle had a zeta potential of approximately +60 mV and the particle size was approximately 135 nm. The particle was stable at different biological pH values and temperatures and high protein loading efficiency was observed. The fluorescent image results revealed that large numbers of particles were taken up into the mammalian cells and escaped from the endosomes into the cytoplasm. In a mouse C26 cell-xenograft cancer model, particles accumulated in cancer cells. In conclusion, the PEI-modified gelatin particle may provide a biodegradable and highly efficient protein delivery system for use in regenerative medicine and cancer therapy.
Nanogels for Pharmaceutical and Biomedical Applications and Their Fabrication Using 3D Printing Technologies
Authors: Cho Hyunah , Jammalamadaka Udayabhanu , Tappa Karthik
Published: February 2018

Nanogels are hydrogels formed by connecting nanoscopic micelles dispersed in an aqueous medium, which give an opportunity for incorporating hydrophilic payloads to the exterior of the micellar networks and hydrophobic payloads in the core of the micelles. Biomedical and pharmaceutical applications of nanogels have been explored for tissue regeneration, wound healing, surgical device, implantation, and peroral, rectal, vaginal, ocular, and transdermal drug delivery. Although it is still in the early stages of development, due to the increasing demands of precise nanogel production to be utilized for personalized medicine, biomedical applications, and specialized drug delivery, 3D printing has been explored in the past few years and is believed to be one of the most precise, efficient, inexpensive, customizable, and convenient manufacturing techniques for nanogel production.
Tunable Bandgap and Optical Properties of Black Phosphorene Nanotubes
Authors: Li Chunmei , Xie Zhongjing , Chen Zhiqian , Cheng Nanpu , Wang Jinghui , Zhu Guoan
Published: February 2018

Black phosphorus (BP), a new two-dimensional material, has been the focus of scientists’ attention. BP nanotubes have potential in the field of optoelectronics due to their low-dimensional effects. In this work, the bending strain energy, electronic structure, and optical properties of BP nanotubes were investigated by using the first-principles method based on density functional theory. The results show that these properties are closely related to the rolling direction and radius of the BP nanotube. All the calculated BP nanotube properties show direct bandgaps, and the BP nanotubes with the same rolling direction express a monotone increasing trend in the value of bandgap with a decrease in radius, which is a stacking effect of the compression strain on the inner atoms and the tension strain on the outer atoms. The bending strain energy of the zigzag phosphorene nanotubes (zPNTs) is higher than that of armchair phosphorene nanotubes (aPNT) with the same radius of curvature due to the anisotropy of the BP’s structure. The imaginary part of the dielectric function, the absorption range, reflectivity, and the imaginary part of the refractive index of aPNTs have a wider range than those of zPNTs, with higher values overall. As a result, tunable BP nanotubes are suitable for optoelectronic devices, such as lasers and diodes, which function in the infrared and ultra-violet regions, and for solar cells and photocatalysis.
A Dislocation-Scale Characterization of the Evolution of Deformation Microstructures around Nanoindentation Imprints in a TiAl Alloy
Authors: Guitton Antoine , Kriaa Hana , Bouzy Emmanuel , Guyon Julien , Maloufi Nabila
Published: February 2018

In this work, plastic deformation was locally introduced at room temperature by nanoindentation on a γ-TiAl-based alloy. Comprehensive analyses of microstructures were performed before and after deformation. In particular, the Burgers vectors, the line directions, and the mechanical twinning systems were studied via accurate electron channeling contrast imaging. Accommodation of the deformation are reported and a scenario is proposed. All features help to explain the poor ductility of the TiAl-based alloys at room temperature.
Computational and Experimental Mechanical Modelling of a Composite Grouted Splice Sleeve Connector System
Authors: Kuang Zhiping , Zheng Guanyu
Published: February 2018

Owing to its controllable tolerance, simple operation and no need for welding at construction site, the composite system involving grouted cement material, steel material and ductile iron material is widely used as grouted splice sleeve (GSS) connector for connecting precast concrete structures. However, the current design recommendations for such a composite connection system do not accurately account for its material nonlinearity behavior. In the present study, a three-dimensional nonlinear finite element model of a GSS connector is developed by considering the nonlinear material behavior of each component to fully investigate its mechanical performance under axial tension. To validate the proposed computational model and demonstrate the nonlinear response of the GSS connector, the pullout experimental test of two engineering specimens is carried out under monotonic tensile load, and a good agreement between the numerical and experimental test results is observed. Then, the sensitivity analysis of some controlling material properties and geometrical parameters is performed using the validated computational model to further understand the performance of such a composite structure in load carrying capacity and ductility of the connections to meet the rapid engineering applications of precast concrete structures.
TiO2@PEI-Grafted-MWCNTs Hybrids Nanocomposites Catalysts for CO2 Photoreduction
Authors: Fusco Caterina , Casiello Michele , Catucci Lucia , Comparelli Roberto , Cotugno Pietro , Falcicchio Aurelia , Fracassi Francesco , Margiotta Valerio , Moliterni Anna , Petronella Francesca , D’Accolti Lucia , Nacci Angelo
Published: February 2018

Anatase (TiO2) and multiwalled carbon nanotubes bearing polyethylenimine (PEI) anchored on their surface were hybridized in different proportions according to a sol-gel method. The resulting nanocomposites (TiO2@PEI-MWCNTs), characterized by BET, XRD, XPS, SEM, and UV techniques, were found efficient catalysts for CO2 photoreduction into formic and acetic acids in water suspension and under visible light irradiation. PEI-grafted nanotubes co-catalysts are believed to act as CO2 activators by forming a carbamate intermediate allowing to accomplish the first example in the literature of polyamines/nanotubes/TiO2 mediated CO2 photoreduction to carboxylic acids.
Layup Configuration Effect on Notch Residual Strength in Composite Laminates
Authors: Santhanakrishnan Balakrishnan Venkateswaran , Seidlitz Holger , Weiß Sabine
Published: February 2018

The current trend shows an increasing demand for composites due to their high stiffness to weight ratio and the recent progress in manufacturing and cost reduction of composites. To combine high strength and stiffness in a cost-effective way, composites are often joined with steel or aluminum. However, joining of thermoset composite materials is challenging because circular holes are often used to join them with their metal counterparts. These design based circular holes induce high stress concentration around the hole. The purpose of this paper is to focus on layup configuration and its impact on notch stress distribution. To ensure high quality and uniformity, the holes were machined by a 5 kW continuous wave (cw) CO2 laser. The stress distribution was evaluated and compared by using finite element analysis and Lekhnitskii’s equations. For further understanding, the notch strength of the laminates was compared and strain distributions were analyzed using the digital image correlation technique.
An Innovative Approach to Control Steel Reinforcement Corrosion by Self-Healing
Authors: Koleva Dessi A.
Published: February 2018

The corrosion of reinforced steel, and subsequent reinforced concrete degradation, is a major concern for infrastructure durability. New materials with specific, tailor-made properties or the establishment of optimum construction regimes are among the many approaches to improving civil structure performance. Ideally, novel materials would carry self-repairing or self-healing capacities, triggered in the event of detrimental influence and/or damage. Controlling or altering a material’s behavior at the nano-level would result in traditional materials with radically enhanced properties. Nevertheless, nanotechnology applications are still rare in construction, and would break new ground in engineering practice. An approach to controlling the corrosion-related degradation of reinforced concrete was designed as a synergetic action of electrochemistry, cement chemistry and nanotechnology. This contribution presents the concept of the approach, namely to simultaneously achieve steel corrosion resistance and improved bulk matrix properties. The technical background and challenges for the application of polymeric nanomaterials in the field are briefly outlined in view of this concept, which has the added value of self-healing. The credibility of the approach is discussed with reference to previously reported outcomes, and is illustrated via the results of the steel electrochemical responses and microscopic evaluations of the discussed materials.
The Anti-Cancer Effects of Frondoside A
Authors: Adrian Thomas E. , Collin Peter
Published: February 2018

Frondoside A is a triterpenoid glycoside from the Atlantic Sea Cucumber, Cucumaria frondosa. Frondoside A has a broad spectrum of anti-cancer effects, including induction of cellular apoptosis, inhibition of cancer cell growth, migration, invasion, formation of metastases, and angiogenesis. In cell lines and animal models studied to date, the anti-cancer effects of the compound are seen in all solid cancers, lymphomas, and leukemias studied to date. These effects appear to be due to potent inhibition of p21-activated kinase 1 (PAK1), which is up-regulated in many cancers. In mouse models, frondoside A has synergistic effects with conventional chemotherapeutic agents, such as gemcitabine, paclitaxel, and cisplatin. Frondoside A administration is well-tolerated. No side effects have been reported and the compound has no significant effects on body weight, blood cells, or on hepatic and renal function tests after long-term administration. Frondoside A may be valuable in the treatment of malignancies, either as a single agent or in combination with other therapeutic modalities.
First Report on Chitin in a Non-Verongiid Marine Demosponge: The Mycale euplectellioides Case
Authors: Żółtowska-Aksamitowska Sonia , Shaala Lamiaa A. , Youssef Diaa T. A. , Elhady Sameh S. , Tsurkan Mikhail V. , Petrenko Iaroslav , Wysokowski Marcin , Tabachnick Konstantin , Meissner Heike , Ivanenko Viatcheslav N. , Bechmann Nicole , Joseph Yvonne , Jesionowski Teofil , Ehrlich Hermann
Published: February 2018

Sponges (Porifera) are recognized as aquatic multicellular organisms which developed an effective biochemical pathway over millions of years of evolution to produce both biologically active secondary metabolites and biopolymer-based skeletal structures. Among marine demosponges, only representatives of the Verongiida order are known to synthetize biologically active substances as well as skeletons made of structural polysaccharide chitin. The unique three-dimensional (3D) architecture of such chitinous skeletons opens the widow for their recent applications as adsorbents, as well as scaffolds for tissue engineering and biomimetics. This study has the ambitious goal of monitoring other orders beyond Verongiida demosponges and finding alternative sources of naturally prestructured chitinous scaffolds; especially in those demosponge species which can be cultivated at large scales using marine farming conditions. Special attention has been paid to the demosponge Mycale euplectellioides (Heteroscleromorpha: Poecilosclerida: Mycalidae) collected in the Red Sea. For the first time, we present here a detailed study of the isolation of chitin from the skeleton of this sponge, as well as its identification using diverse bioanalytical tools. Calcofluor white staining, Fourier-transform Infrared Spcetcroscopy (FTIR), electrospray ionization mass spectrometry (ESI-MS), scanning electron microscopy (SEM), and fluorescence microscopy, as well as a chitinase digestion assay were applied in order to confirm with strong evidence the finding of a-chitin in the skeleton of M. euplectellioides. We suggest that the discovery of chitin within representatives of the Mycale genus is a promising step in their evaluation of these globally distributed sponges as new renewable sources for both biologically active metabolites and chitin, which are of prospective use for pharmacology and biomaterials oriented biomedicine, respectively.
Comparative Effect of Mo and Cr on Microstructure and Mechanical Properties in NbV-Microalloyed Bainitic Steels
Authors: Kostryzhev Andrii , Singh Navjeet , Chen Liang , Killmore Chris , Pereloma Elena
Published: February 2018

Steel product markets require the rolled stock with further increasing mechanical properties and simultaneously decreasing price. The steel cost can be reduced via decreasing the microalloying elements contents, although this decrease may undermine the mechanical properties. Multi-element microalloying with minor additions is the route to optimise steel composition and keep the properties high. However, this requires deep understanding of mutual effects of elements on each other’s performance with respect to the development of microstructure and mechanical properties. This knowledge is insufficient at the moment. In the present work we investigate the microstructure and mechanical properties of bainitic steels microalloyed with Cr, Mo, Nb and V. Comparison of 0.2 wt. % Mo and Cr additions has shown a more pronounced effect of Mo on precipitation than on phase balance. Superior strength of the MoNbV-steel originated from the strong solid solution strengthening effect. Superior ductility of the CrNbV-steel corresponded to the more pronounced precipitation in this steel. Nature of these mechanisms is discussed.
Effect of Nitric and Oxalic Acid Addition on Hard Anodizing of AlCu4Mg1 in Sulphuric Acid
Authors: Sieber Maximilian , Morgenstern Roy , Scharf Ingolf , Lampke Thomas
Published: February 2018

The anodic oxidation process is an established means for the improvement of the wear and corrosion resistance of high-strength aluminum alloys. For high-strength aluminum-copper alloys of the 2000 series, both the current efficiency of the anodic oxidation process and the hardness of the oxide coatings are significantly reduced in comparison to unalloyed substrates. With regard to this challenge, recent investigations have indicated a beneficial effect of nitric acid addition to the commonly used sulphuric acid electrolytes both in terms of coating properties and process efficiency. The present work investigates the anodic oxidation of the AlCu4Mg1 alloy in a sulphuric acid electrolyte with additions of nitric acid as well as oxalic acid as a reference in a full-factorial design of experiments (DOE). The effect of the electrolyte composition on process efficiency, coating thickness and hardness is established by using response functions. A mechanism for the participation of the nitric acid additive during the oxide formation is proposed. The statistical significance of the results is assessed by an analysis of variance (ANOVA). Eventually, scratch testing is applied in order to evaluate the failure mechanisms and the abrasion resistance of the obtained conversion coatings.
Mini-EmulsionFabricated Magnetic and Fluorescent Hybrid Janus Micro-Motors
Authors: Jiao Jiapu , Xu Dandan , Liu Yuhuan , Zhao Weiwei , Zhang Jiaheng , Zheng Tingting , Feng Huanhuan , Ma Xing
Published: February 2018

Self-propelling micro/nano-motors have attracted great attention due to their controllable active motion and various functional attributes. To date, a variety of technologies have been reported for the fabrication of micro/nano-motors. However, there are still several challenges that need to be addressed. One of them is to endow micro/nano-motors with multi-functionalities by a facile fabrication process. Here, we present a universal approach, adopted from the emulsion templating method, for the fabrication of Janus micro-motors. With a one-step process, magnetic nanoparticles and fluorescent dyes are simultaneously embedded into the microparticles. The self-propelled motors can be used as an active label or fluorescent tracer through manipulation of their motion using magnetic guidance.
Characterizing Sources of Small DC Motor Noise and Vibration
Authors: Cho Yong Thung
Published: February 2018

Small direct current (DC) motors are widely used due to their low cost and compact structure. Small DC motors of various designs are available on the market in different sizes. The smaller the motor, the more closely it may be used by individuals. Contrary to the size and simplicity of these motors in terms of structural design, sources of motor noise and vibration can be quite diverse and complicated. In this study, the source of motor noise and vibration was visualized over a very wide range of frequencies. The particle velocity of the motor was reconstructed from nearfield sound pressure measurements of motor noise. In addition to noncontact measurements conducted on a motor running at constant speed, the particle velocity of a stationary motor due to the impulse of an impact hammer was measured with an accelerometer. Furthermore, motor noise was measured under motor run-up conditions with different rotational speeds. As a result, by combination of these three methods, the sources of motor noise were accurately identified over a wide range of frequencies.
Lattice Boltzmann Simulation of the Hydrodynamic Entrance Region of Rectangular Microchannels in the Slip Regime
Authors: Ma Niya , Duan Zhipeng , Ma Hao , Su Liangbin , Liang Peng , Ning Xiaoru , He Boshu , Zhang Xin
Published: February 2018

Developing a three-dimensional laminar flow in the entrance region of rectangular microchannels has been investigated in this paper. When the hydrodynamic development length is the same magnitude as the microchannel length, entrance effects have to be taken into account, especially in relatively short ducts. Simultaneously, there are a variety of non-continuum or rarefaction effects, such as velocity slip and temperature jump. The available data in the literature appearing on this issue is quite limited, the available study is the semi-theoretical approximate model to predict pressure drop of developing slip flow in rectangular microchannels with different aspect ratios. In this paper, we apply the lattice Boltzmann equation method (LBE) to investigate the developing slip flow through a rectangular microchannel. The effects of the Reynolds number (1 < Re < 1000), channel aspect ratio (0 < ε < 1), and Knudsen number (0.001 < Kn < 0.1) on the dimensionless hydrodynamic entrance length, and the apparent friction factor, and Reynolds number product, are examined in detail. The numerical solution of LBM can recover excellent agreement with the available data in the literature, which proves its accuracy in capturing fundamental fluid characteristics in the slip-flow regime.
Light-Controlled Swarming and Assembly of Colloidal Particles
Authors: Zhang Jianhua , Guo Jingjing , Mou Fangzhi , Guan Jianguo
Published: February 2018

Swarms and assemblies are ubiquitous in nature and they can perform complex collective behaviors and cooperative functions that they cannot accomplish individually. In response to light, some colloidal particles (CPs), including light active and passive CPs, can mimic their counterparts in nature and organize into complex structures that exhibit collective functions with remote controllability and high temporospatial precision. In this review, we firstly analyze the structural characteristics of swarms and assemblies of CPs and point out that light-controlled swarming and assembly of CPs are generally achieved by constructing light-responsive interactions between CPs. Then, we summarize in detail the recent advances in light-controlled swarming and assembly of CPs based on the interactions arisen from optical forces, photochemical reactions, photothermal effects, and photoisomerizations, as well as their potential applications. In the end, we also envision some challenges and future prospects of light-controlled swarming and assembly of CPs. With the increasing innovations in mechanisms and control strategies with easy operation, low cost, and arbitrary applicability, light-controlled swarming and assembly of CPs may be employed to manufacture programmable materials and reconfigurable robots for cooperative grasping, collective cargo transportation, and micro- and nanoengineering.
Structural Transition of Inorganic Silica–Carbonate Composites Towards Curved Lifelike Morphologies
Authors: Opel Julian , Kellermeier Matthias , Sickinger Annika , Morales Juan , Cölfen Helmut , García-Ruiz Juan-Manuel
Published: February 2018

The self-assembly of alkaline earth carbonates in the presence of silica at high pH leads to a unique class of composite materials displaying a broad variety of self-assembled superstructures with complex morphologies. A detailed understanding of the formation process of these purely inorganic architectures is crucial for their implications in the context of primitive life detection as well as for their use in the synthesis of advanced biomimetic materials. Recently, great efforts have been made to gain insight into the molecular mechanisms driving self-assembly in these systems, resulting in a consistent model for morphogenesis at ambient conditions. In the present work, we build on this knowledge and investigate the influence of temperature, supersaturation, and an added multivalent cation as parameters by which the shape of the forming superstructures can be controlled. In particular, we focus on trumpet- and coral-like structures which quantitatively replace the well-characterised sheets and worm-like braids at elevated temperature and in the presence of additional ions, respectively. The observed morphological changes are discussed in light of the recently proposed formation mechanism with the aim to ultimately understand and control the major physicochemical factors governing the self-assembly process.
Effect of Atomic Charges on Octanol–Water Partition Coefficient Using Alchemical Free Energy Calculation
Authors: Ogata Koji , Hatakeyama Makoto , Nakamura Shinichiro
Published: February 2018

The octanol–water partition coefficient (logPow) is an important index for measuring solubility, membrane permeability, and bioavailability in the drug discovery field. In this paper, the logPow values of 58 compounds were predicted by alchemical free energy calculation using molecular dynamics simulation. In free energy calculations, the atomic charges of the compounds are always fixed. However, they must be recalculated for each solvent. Therefore, three different sets of atomic charges were tested using quantum chemical calculations, taking into account vacuum, octanol, and water environments. The calculated atomic charges in the different environments do not necessarily influence the correlation between calculated and experimentally measured ∆Gwater values. The largest correlation coefficient values of the solvation free energy in water and octanol were 0.93 and 0.90, respectively. On the other hand, the correlation coefficient of logPow values calculated from free energies, the largest of which was 0.92, was sensitive to the combination of the solvation free energies calculated from the calculated atomic charges. These results reveal that the solvent assumed in the atomic charge calculation is an important factor determining the accuracy of predicted logPow values.
Semi-Preparative Separation of 10 Caffeoylquinic Acid Derivatives Using High Speed Counter-Current Chromatogaphy Combined with Semi-Preparative HPLC from the Roots of Burdock (Arctium lappa L.)
Authors: Zheng Zhenjia , Wang Xiao , Liu Pengli , Li Meng , Dong Hongjing , Qiao Xuguang
Published: February 2018

Burdock roots are healthy dietary supplements and a kind of famous traditional Chinese medicine, which contains large amounts of caffeoylquinic acid derivatives. However, little research has been reported on the preparative separation of these compounds from burdock roots. In the present study, a combinative method of HSCCC and semi-preparative HPLC was developed for the semi-preparative separation of caffeoylquinic acid derivatives from the burdock roots. The ethyl acetate extract of burdock roots was first fractionated by MCI macroporous resin chromatography and give three fractions (Fr. 1–3) from the elution of 40% methanol. Then, these three fractions (120 mg) were separately subjected to HSCCC for purification with the solvent system composed of petroleum ether-ethyl acetate-methanol-water at different volume ratios, and the mixtures were further purified by semi-preparative HPLC. As a result, a total of eight known caffeoylquinic acid derivatives including 3-O-caffeoylquinic acid (32.7 mg, 95.7%), 1,5-O- dicaffeoylquinic acid (4.3 mg, 97.2%), 3-O-caffeoylquinic acid methyl ester (12.1 mg, 93.2%), 1,3-O-dicaffeoylquinic acid (42.9 mg, 91.1%), 1,5-O-dicaffeoyl-3-O-(4-maloyl)-quinic acid (4.3 mg, 84.5%), 4,5-O-dicaffeoylquinic acid (5.3 mg, 95.5%), 1,5-O-dicaffeoyl-3-O-succinylquinic acid (8.7 mg, 93.4%), and 1,5-O-dicaffeoyl-4-O-succinylquinic acid (1.7 mg, 91.8%), and two new compounds were obtained. The new compounds were 1,4-O-dicaffeoyl-3-succinyl methyl ester quinic acid (14.6 mg, 96.1%) and 1,5-O-dicaffeoyl-3-O-succinyl methyl ester quinic acid (3.1 mg, 92.6%), respectively. The research indicated that the combination of HSCCC and semi-preparative HPLC is a highly efficient approach for preparative separation of the instability and bioactive caffeoylquinic acid derivatives from natural products.
Pd-Catalyzed, Highly Selective C(sp2)-Br Bond Coupling Reactions of o-(or m-, or p-) Chloromethyl Bromobenzene with Arylboronic Acids
Authors: Pei Ming-ming , Liu Ping , Liu Yan , Lv Xin-ming , Ma Xiao-wei , Dai Bin
Published: February 2018

Highly selective C(sp2)–C(sp2) cross-coupling of dihalogenated hydrocarbons comprising C(sp2)–Br and C(sp3)–Cl bonds with arylboronic acids is reported. This highly selective coupling reaction of the C(sp2)–Br bond is successfully achieved using Pd(OAc)2 and PCy3·HBF4 as the palladium source and ligand, respectively. A series of chloromethyl-1,1′-biphenyl compounds are obtained in moderate-to-excellent yields. Moreover, this protocol can be extended to the one-pot dual arylation of 1-bromo-4-(chloromethyl)benzene with two arylboronic acids, leading to diverse unsymmetrical 4-benzyl-1,1′-biphenyl derivatives.
Dynamic Changes in Phenolics and Antioxidant Capacity during Pecan (Carya illinoinensis) Kernel Ripening and Its Phenolics Profiles
Authors: Jia Xiaodong , Luo Huiting , Xu Mengyang , Zhai Min , Guo Zhongren , Qiao Yushan , Wang Liangju
Published: February 2018

Pecan (Carya illinoinensis) kernels have a high phenolics content and a high antioxidant capacity compared to other nuts—traits that have attracted great interest of late. Changes in the total phenolic content (TPC), condensed tannins (CT), total flavonoid content (TFC), five individual phenolics, and antioxidant capacity of five pecan cultivars were investigated during the process of kernel ripening. Ultra-performance liquid chromatography coupled with quadruple time-of-flight mass (UPLC-Q/TOF-MS) was also used to analyze the phenolics profiles in mixed pecan kernels. TPC, CT, TFC, individual phenolics, and antioxidant capacity were changed in similar patterns, with values highest at the water or milk stages, lowest at milk or dough stages, and slightly varied at kernel stages. Forty phenolics were tentatively identified in pecan kernels, of which two were first reported in the genus Carya, six were first reported in Carya illinoinensis, and one was first reported in its kernel. The findings on these new phenolic compounds provide proof of the high antioxidant capacity of pecan kernels.
Probing the Influence of Linker Length and Flexibility in the Design and Synthesis of New Trehalase Inhibitors
Authors: D’Adamio Giampiero , Forcella Matilde , Fusi Paola , Parenti Paolo , Matassini Camilla , Ferhati Xhenti , Vanni Costanza , Cardona Francesca
Published: February 2018

This work aims to synthesize new trehalase inhibitors selective towards the insect trehalase versus the porcine trehalase, in view of their application as potentially non-toxic insecticides and fungicides. The synthesis of a new pseudodisaccharide mimetic 8, by means of a stereoselective α-glucosylation of the key pyrrolizidine intermediate 13, was accomplished. The activity of compound 8 as trehalase inhibitor towards C. riparius trehalase was evaluated and the results showed that 8 was active in the μM range and showed a good selectivity towards the insect trehalase. To reduce the overall number of synthetic steps, simpler and more flexible disaccharide mimetics 9–11 bearing a pyrrolidine nucleus instead of the pyrrolizidine core were synthesized. The biological data showed the key role of the linker chain’s length in inducing inhibitory properties, since only compounds 9 (α,β-mixture), bearing a two-carbon atom linker chain, maintained activity as trehalase inhibitors. A proper change in the glucosyl donor-protecting groups allowed the stereoselective synthesis of the β-glucoside 9β, which was active in the low micromolar range (IC50 = 0.78 μM) and 12-fold more potent (and more selective) than 9α towards the insect trehalase.
Asymmetric Synthesis of Spirooxindoles via Nucleophilic Epoxidation Promoted by Bifunctional Organocatalysts
Authors: Miceli Martina , Mazziotta Andrea , Palumbo Chiara , Roma Elia , Tosi Eleonora , Longhi Giovanna , Abbate Sergio , Lupattelli Paolo , Mazzeo Giuseppe , Gasperi Tecla
Published: February 2018

Taking into account the postulated reaction mechanism for the organocatalytic epoxidation of electron-poor olefins developed by our laboratory, we have investigated the key factors able to positively influence the H-bond network installed inside the substrate/catalyst/oxidizing agent. With this aim, we have: (i) tested a few catalysts displaying various effects that noticeably differ in terms of steric hindrance and electron demand; (ii) employed α-alkylidene oxindoles decorated with different substituents on the aromatic ring (11a–g), the exocylic double bond (11h–l), and the amide moiety (11m–v). The observed results suggest that the modification of the electron-withdrawing group (EWG) weakly conditions the overall outcomes, and conversely a strong influence is unambiguously ascribable to either the N-protected or N-unprotected lactam framework. Specifically, when the NH free substrates (11m–u) are employed, an inversion of the stereochemical control is observed, while the introduction of a Boc protecting group affords the desired product 12v in excellent enantioselectivity (97:3 er).
Controlled and Efficient Polymerization of Conjugated Polar Alkenes by Lewis Pairs Based on Sterically Hindered Aryloxide-Substituted Alkylaluminum
Authors: Wang Xiaojun , Zhang Yixin , Hong Miao
Published: February 2018

Reported herein is the development of an effective strategy for controlled and efficient Lewis pair polymerization of conjugated polar alkenes, including methyl methacrylate (MMA), n-butyl methacrylate (nBuMA), and γ-methyl-α-methylene-γ-butyrolactone (γMMBL), by the utilization of sterically encumbered Al(BHT)2Me (BHT: 2,6-di-tert-butyl-4-methylphenol) as a Lewis acid that shuts down intramolecular backbiting termination. In combination with a selected N-heterocyclic carbene (NHC) as a Lewis base, the polymerization of MMA exhibited activity up to 3000 h−1 TOF and an acceptable initiation efficiency of 60.6%, producing polymers with high molecular weight (Mn up to 130 kg/mol) and extremely narrow dispersity (Đ = 1.06~1.13). This controlled polymerization with a living characteristic has been evidenced by chain-extension experiments and chain-end analysis, and enabled the synthesis of well-defined diblock copolymers.
Overexpression of Receptor Tyrosine Kinase EphB4 Triggers Tumor Growth and Hypoxia in A375 Melanoma Xenografts: Insights from Multitracer Small Animal Imaging Experiments
Authors: Neuber Christin , Belter Birgit , Meister Sebastian , Hofheinz Frank , Bergmann Ralf , Pietzsch Hans-Jürgen , Pietzsch Jens
Published: February 2018

Experimental evidence has associated receptor tyrosine kinase EphB4 with tumor angiogenesis also in malignant melanoma. Considering the limited in vivo data available, we have conducted a systematic multitracer and multimodal imaging investigation in EphB4-overexpressing and mock-transfected A375 melanoma xenografts. Tumor growth, perfusion, and hypoxia were investigated by positron emission tomography. Vascularization was investigated by fluorescence imaging in vivo and ex vivo. The approach was completed by magnetic resonance imaging, radioluminography ex vivo, and immunohistochemical staining for blood and lymph vessel markers. Results revealed EphB4 to be a positive regulator of A375 melanoma growth, but a negative regulator of tumor vascularization. Resulting in increased hypoxia, this physiological characteristic is considered as highly unfavorable for melanoma prognosis and therapy outcome. Lymphangiogenesis, by contrast, was not influenced by EphB4 overexpression. In order to distinguish between EphB4 forward and EphrinB2, the natural EphB4 ligand, reverse signaling a specific EphB4 kinase inhibitor was applied. Blocking experiments show EphrinB2 reverse signaling rather than EphB4 forward signaling to be responsible for the observed effects. In conclusion, functional expression of EphB4 is considered a promising differentiating characteristic, preferentially determined by non-invasive in vivo imaging, which may improve personalized theranostics of malignant melanoma.
Efficiency of Osmotic Dehydration of Apples in Polyols Solutions
Authors: Cichowska Joanna , Żubernik Joanna , Czyżewski Jakub , Kowalska Hanna , Witrowa-Rajchert Dorota
Published: February 2018

The present study aimed to evaluate the influence of selected compounds from the polyol group, as well as other saccharides, on the osmotic dehydration process of apples. The following alternative solutions were examined: erythritol, xylitol, maltitol, inulin and oligofructose. Efficiency of the osmotic dehydration process was evaluated based on the kinetics of the process, and through comparison of the results obtained during the application of a sucrose solution. This innovative research utilizes alternative solutions in osmotic pretreatment, which until now, have not been commonly used in fruit processing by researchers worldwide. Results indicate that erythritol and xylitol show stronger or similar efficiency to sucrose; however, the use of inulin, as well as oligofructose, was not satisfactory due to the insufficient, small osmotic driving forces of the process, and the low values of mass transfer parameters.
Docosahexaenoic Acid Helps to Lessen Extinction Memory in Rats
Authors: Hashimoto Michio , Hossain Shahdat , Katakura Masanori , Mamun Abdullah Al , Shido Osamu
Published: February 2018

Abstract: Memory extinction is referred to as a learning process in which a conditioned response (CR) progressively reduces over time as an animal learns to uncouple a response from a stimulus. Extinction occurs when the rat is placed into a context without shock after training. Docosahexaenoic acid (DHA, C22:6, n-3) is implicated in memory formation in mammalian brains. In a two-way active shuttle-avoidance apparatus, we examined whether DHA affects the extinction memory and the expression of brain cognition-related proteins, including gastrin-releasing peptide receptor (GRPR), brain-derived neurotrophic factor receptor (BDNFR) tyrosine kinase receptor B (TrKB), and N-methyl-d-aspartate receptor (NMDAR) subunits NR2A and NR2B. Also, the protein levels of GRP, BDNF, postsynaptic density protein-95 (PSD-95), and vesicular acetylcholine transporter (VAChT), and the antioxidative potentials, in terms of lipid peroxide (LPO) and reactive oxygen species (ROS), were examined in the hippocampus. During the acquisition phase, the rats received a conditioned stimulus (CS-tone) paired with an unconditioned stimulus (UCS foot shock) for three consecutive days (Sessions S1, S2, and S3, each consisting of 30-trials) after 12 weeks of oral administration of DHA. After a three-day interval, the rats were re-subjected to two extinction sessions (S4, S5), each comprising 30 trials of CS alone. During the acquisition training in S1, the shock-related avoidance frequency (acquisition memory) was significantly higher in the DHA-administered rats compared with the control rats. The avoidance frequency, however, decreased with successive acquisition trainings in sessions S2 and S3. When the rats were subjected to the extinction sessions after a break for consolidation, the conditioned response (CR) was also significantly higher in the DHA-administered rats. Interestingly, the freezing responses (frequency and time) also significantly decreased in the DHA-administered rats, thus suggesting that a higher coping capacity was present during fear stress in the DHA-administered rats. DHA treatments increased the mRNA levels of GRPR, BDNF receptor TrKB, and NMDAR subunit NR2B. DHA also increased the protein levels of GRP, BDNF, PSD-95, and VAChT, and the antioxidative potentials in the hippocampus. These results suggest the usefulness of DHA for treating stress disorders.