bluuebunny/crossref_metadata_2025_split huggingface dataset:
Intracellular Chemistry: Integrating Molecular Inorganic Catalysts with Living Systems
Authors: Ngo Anh H. , Bose Sohini , Do Loi H. 
Published: March 2018

AbstractThis concept article focuses on the rapid growth of intracellular chemistry dedicated to the integration of small‐molecule metal catalysts with living cells and organisms. Although biological systems contain a plethora of biomolecules that can deactivate inorganic species, researchers have shown that small‐molecule metal catalysts could be engineered to operate in heterogeneous aqueous environments. Synthetic intracellular reactions have recently been reported for olefin hydrogenation, hydrolysis/oxidative cleavage, azide‐alkyne cycloaddition, allylcarbamate cleavage, C−C bond cross coupling, and transfer hydrogenation. Other promising targets for new biocompatible reaction discovery will also be discussed, with a special emphasis on how such innovations could lead to the development of novel technologies and chemical tools.
Phosphorescence Through Hindered Motion of Pure Organic Emitters
Authors: Hayduk Matthias , Riebe Steffen , Voskuhl Jens 
Published: March 2018

AbstractThis minireview deals with the phenomenon of room‐temperature phosphorescence induced by aggregation or crystallisation. Recent achievements, as well as novel classes of these unique luminophores, are put in to focus. In this fashion, different compounds, which reveal delayed fluorescence or phosphorescence upon fixation in a crystal lattice or within aggregates are described. Furthermore, the photophysical properties, the origin of the long‐lived triplet states, and the possible applications of these fascinating classes of molecules are also discussed. To conclude, a short overview about the state of art in the field of pure organic phosphors at room temperature is presented.
Electrocatalytic Hydroxylation of Sterols by Steroid C25 Dehydrogenase from Sterolibacterium denitrificans
Authors: Kalimuthu Palraj , Wojtkiewicz Agnieszka M. , Szaleniec Maciej , Bernhardt Paul V. 
Published: March 2018

AbstractThe electrochemically driven catalysis of the complex molybdoenzyme steroid C25 dehydrogenase (S25DH) from the β‐Proteobacterium Sterolibacterium denitrificans is reported. S25DH catalyses the oxygen‐independent regioselective hydroxylation of the tertiary C25 atom of sterols and also their derivatives. Cholest‐4‐en‐3‐one is a native substrate for S25DH, which produces 25‐hydroxycholest‐4‐en‐3‐one as a product of catalytic turnover. Cholecalciferol (vitD3) is also a substrate. S25DH was immobilised on a modified gold working electrode with the co‐adsorbent chitosan. The complexes ferricyanide ([Fe(CN)6]3−) and ferrocenium methanol (FM+) are effective artificial electron acceptors from S25DH and act as mediators of electron transfer between the electrode and the enzyme. 2‐Hydroxypropyl‐β‐cyclodextrin (HPCD) was employed as a sterol solubiliser, in addition to 2‐methoxyethanol. The catalytic activity varied, depending upon the concentration of solubiliser in the reaction mixture. Parallel studies with [Fe(CN)6]3− as a chemical (as opposed to electrochemical) oxidant coupled to HPLC analysis show that S25DH is capable of oxidising both vitD3 and its less stable isomer, pre‐vitD3, and that the former substrate is stabilised by HPCD.
Synthesis and Characterization of Photothermal Osmium Carbolong Complexes
Authors: Lin Qin , Li Shenyan , Lin Jianfeng , Chen Meijin , Lu Zhengyu , Tang Chun , Chen Zhixin , He Xumin , Chen Jiangxi , Xia Haiping 
Published: March 2018

AbstractMetallacycles with chelating polydentate conjugated‐carbon chain ligands are called carbolong complexes, which are expected to have interesting properties. In this work, the preparation of 12‐carbon carbolong complexes in which all of the coordinated atoms in the equatorial plane are carbon atoms was studied. With the help of the well‐established mechanism, a new approach to prepare coplanar carbolong complexes bearing different organic functional groups was developed by adding different terminal alkynes in sequence. In the presence of HBF4, these coplanar carbolong complexes were converted to η3‐allyl osmapentalene derivatives, which can be produced directly from the reaction of cyclopropaosmapentalene 1 with terminal alkynes in the presence of AgBF4 under anhydrous conditions. This study offers a new route for the preparation of functional osmium carbolong complexes with excellent photothermal properties, which can be used to prepare photothermal materials.
Ligand‐Based Storage of Protons and Electrons in Dihydrazonopyrrole Complexes of Nickel
Authors: Chang Mu‐Chieh , McNeece Andrew J. , Hill Ethan A. , Filatov Alexander S. , Anderson John S. 
Published: March 2018

AbstractA newly developed dihydrazonopyrrole ligand and corresponding Ni complexes have been synthesized and thoroughly characterized. Electrochemical studies and chemical reactivity tests show that these complexes can reversibly store both electrons and protons, or equivalently H‐atoms, via ligand‐based events. The stored H‐atom equivalent can be transferred to small molecules such as acetonitrile or oxygen. Furthermore, this series of complexes can adopt a variety of different coordination modes. In addition to one e− reactivity, the two e− electrophilic oxidation of phosphines is also demonstrated. Taken together, these results show that dihydrazonopyrrole complexes represent a geometrically and electronically flexible scaffold for controlling the flow of both electrons and protons.
Single‐Molecule Sensing with Nanopore Confinement: From Chemical Reactions to Biological Interactions
Authors: Lin Yao , Ying Yi‐Lun , Gao Rui , Long Yi‐Tao 
Published: March 2018

AbstractThe nanopore can generate an electrochemical confinement for single‐molecule sensing that help understand the fundamental chemical principle in nanoscale dimensions. By observing the generated ionic current, individual bond‐making and bond‐breaking steps, single biomolecule dynamic conformational changes and electron transfer processes that occur within pore can be monitored with high temporal and current resolution. These single‐molecule studies in nanopore confinement are revealing information about the fundamental chemical and biological processes that cannot be extracted from ensemble measurements. In this Concept article, we introduce and discuss the electrochemical confinement effects on single‐molecule covalent reactions, conformational dynamics of individual molecules and host‐guest interactions in protein nanopores. Then, we extend the concept of nanopore confinement effects to confine electrochemical redox reactions in solid‐state nanopores for developing new sensing mechanisms.
Unusually Long‐Wavelength Emissions of Cyclopropanes: New Insight into C−C Bond Homolysis
Authors: Abe Manabu , Kanahara Kousei , Kadowaki Norito , Tan Chun‐Jui , Tsai Hui‐Hsu Gavin 
Published: March 2018

AbstractBond homolysis (BHo) is a fundamental concept in chemical‐bonding phenomena. To date, research studies on the BHo concept have provided crucial information for understanding the nature of chemical bonding and reactions. Two potential‐energy minima, a σ‐bonding isomer and a singlet‐diradical isomer, have been known to exist in carbon–carbon BHo. Herein, a third isomer, that is, a puckered singlet diradical exhibiting unstructured long‐wavelength fluorescence beyond 460 nm, was first observed in the excited states of 1,4‐diarylbicyclo[2.1.0]pentane derivatives. The careful selection of appropriate substituents in the bicyclic structures enabled direct spectral detection. State‐of‐the‐art ab initio quantum chemical calculations quantitatively reproduced the experimental observations. This new finding provides new insight into carbon–carbon bond‐breaking and ‐forming processes.
Therapeutic Nanoreactors as In Vivo Nanoplatforms for Cancer Therapy
Authors: Mukerabigwi Jean Felix , Ge Zhishen , Kataoka Kazunori 
Published: March 2018

AbstractTherapeutic nanoreactors have been proposed as nanoplatforms to treat diseases through in situ production of therapeutic agents. When this treatment strategy is applied in cancer therapy, it can efficiently produce highly toxic anticancer drugs in situ from low‐toxic prodrugs or some biomolecules in tumor tissues, which can maximize the therapeutic efficacy with a significantly low systemic toxicity. An ideal therapeutic nanoreactor can provide the reaction space, protect the loaded fragile catalysts, target the desired pathological site, and be selectively activated. In this minireview, we highlight the recent advances concerning the applications of therapeutic nanoreactors as in vivo nanoplatforms particularly in cancer therapy. Herein, the therapeutic nanoreactors are discussed on the basis of treatment strategies and various nanoparticles. Specifically, the treatment strategies of nanoreactors including single enzyme, single enzyme with chemodrugs, and multienzymes, as well as varying types of engineered nanoparticle‐loaded active catalysts, primarily including liposomes, polymersomes, polymeric micelles, inorganic nanoparticles, and metal–organic framework (MOF) architectures, are documented and briefly discussed. Finally, we elucidate the current challenges to be addressed toward further development and translation into clinical applications of these therapeutic nanoreactors in cancer therapy.
Synthesis of Benzofuranones via Malonates Desymmetrization: Yield Increase by the Portion‐wise Addition of Quinones
Authors: Puglisi Antonio , Giustini Chiara , Ricucci Angela , Perotti Elisa , Massaro Luca , Morra Diego , Ciucci Flavia , Zucchet Alessio , Antenucci Achille , Moliterno Mauro , Placidi Simone , Sciubba Fabio , Galantini Luciano , Salvio Riccardo , Bella Marco 
Published: March 2018

AbstractThe organocatalyzed addition of several malonates to 1,4‐benzoquinones affords benzofuranones bearing a quaternary stereocenter with good enantioselectivity. This reaction is an intramolecular desymmetrization since it proceeds through the formation of an arylated achiral malonate that cyclizes to give the reaction product. The addition rate of the quinone dramatically affects the reaction yield which was originally low. The yield was considerably increased, in some cases, from less than 20 % to over 95 %, by adding the quinone in portions rather than at once, keeping similar enantioselectivity. A possible rationalization for the preferential formation of the indicated enantiomer has been investigated by DFT calculations.
Limitations of Steric Bulk: Towards Phospha‐germynes and Phospha‐stannynes
Authors: Hinz Alexander , Goicoechea Jose M. 
Published: March 2018

AbstractThe use of bulky aryl(silyl)amides (R) as substituents for the stabilisation of phospha‐germynes and phospha‐stannynes (R−Ge≡P and R−Sn≡P, respectively) is described. Such species can be transiently generated by photolysis of the phosphaketene precursors (RE(PCO); E=Ge, Sn). Utilisation of bulky amides R1 and R2 (R1=Ar**NSi(OtBu)3, where Ar**=2,6‐bis[bis(4‐tert‐butylphenyl)methyl]‐4‐methylphenyl; R2=Ar***NSi(iPr)3, where Ar***=2,6‐bis[bis(3,5‐di‐tert‐butylphenyl)methyl]‐4‐methylphenyl) facilitates the formation of diphosphene‐type dimers, [(RGe)P]2 and [(RSn)P]2. In an effort to circumvent dimerisation, the bulkier R3 substituent (R3=Ar***NSi(4‐tert‐butylphenyl)3) was employed in an analogous series of experiments. This affords cyclic germylenes and stannylenes due to insertion of the terminal phosphide into Si−C bonds of the R3 substituent, which in case of the stannylene could act as a trap for another R3−Sn≡P moiety. All attempts to isolate terminal phosphide species were unsuccessful due to the reactivity of such compounds towards the organic periphery of the bulky amides, highlighting the limitations of highly sterically demanding functionalities.
Ferrocenyl Phthalocyanine as Donor in Non‐Poly(3‐hexylthiophen‐2,5‐diyl) Bulk Heterojunction Solar Cell
Authors: Nar Ilgın , Atsay Armağan , Altındal Ahmet , Hamuryudan Esin , Koçak Makbule B. , Gül Ahmet 
Published: March 2018

AbstractBulk heterojunction (BHJ) solar cells might one day play a vital role in realizing low‐cost and environmentally benign photovoltaic devices. In this work, a BHJ solar cell was designed, based on a hexadeca‐substituted phthalocyanine (FcPc) with ferrocenyl linked to the phthalocyanine ring. Next, we sought to obtain more quantitative information about the usability of this newly synthesized compound as a donor material in BHJ solar cells. Thus, BHJs with the structure of indium tin oxide/poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate)/FcPc:[6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) blend/LiF/Al were fabricated and characterized. The effect of blend ratio (0.5–2.0) on the BHJ solar cell parameters was also investigated. Interesting results were obtained in FcPc and the PCBM blend‐based BHJ solar cell under optimized conditions. Our results presented here demonstrate that BHJ devices employing FcPc as a donor has great potential for the development of highly efficient non‐poly(3‐hexylthiophen‐2,5‐diyl) photovoltaic devices.
Colorimetric chiral fluorescent sensors for Eu3+ and sequential enantioselective sensing of malate anion
Authors: Liu Xiaoyan , Wang Peng , Fu Jiaxin , Yao Kun , Chang Yongxin , Xu Kuoxi 
Published: March 2018

AbstractNovel phenanthroline Schiff base fluorescent sensors L1, L2, and D1 were designed and synthesized. The sensing abilities of the compounds in the presence of metal cations (Li+, Na+, K+, Ag+, Mg2+, Ba2+, Ca2+, Mn2+, Pb2+, Hg2+, Ni2+, Zn2+, Cd2+, Co2+, Cu2+, Cr3+, Fe3+, Fe2+, Al3+, and Eu3+) were studied by UV‐vis and fluorescent spectroscopy. The compounds L1, L2, and D1 could act as Eu3+ ion turn‐off fluorescent sensors based on ligand‐to‐metal binding mechanism in DMSO‐H2O solution (v/v = 1:1, 10 mM Tris, pH = 7.4). Additionally, the L1–Eu3+ and D1–Eu3+ complexes could be applied as turn‐on enantioselective sensors sensing of malate anion isomers with color changes. Furthermore, biological experiments using living PC‐12 cells demonstrated that L1 and D1 had excellent membrane permeability and could be used as effective fluorescent sensors for detecting Eu3+ and malate anion in living cells.
Self‐assembly and chiroptical properties in supramolecular complexes of adenosine phosphates and guanidinium‐bispyrene
Authors: Trévisan Marie , Fossépré Mathieu , Paolantoni Delphine , Rubio‐Magnieto Jenifer , Dumy Pascal , Ulrich Sébastien , Surin Mathieu 
Published: March 2018

AbstractSupramolecular systems that respond to the hydrolysis of adenosine phosphates (APs) are attractive for biosensing and to fabricate bioinspired self‐assembled materials. Here, we report on the formation of supramolecular complexes between an achiral guanidinium derivative bearing two pyrene moieties, with each of the three adenosine phosphates: AMP, ADP, and ATP. By combining results from circular dichroism spectroscopy and molecular modeling simulations, we explore the induced chirality, the dynamics of the complexes, and the interactions at play, which altogether provide insights into the supramolecular self‐assembly between APs and the guanidinium‐bispyrene. Finally, we identify the chiroptical signals of interest in mixtures of the guanidinium derivative with the three APs in different proportions. This study constitutes a basis to evolve toward a chiroptical detection of the hydrolysis of APs based on organic supramolecular probes.
A Study on Thermodiffusion in Ternary Liquid Mixtures Using Enhanced Molecular Dynamics Algorithm with Experimental Validation
Authors: Mozaffari Seyedeh Hoda , Srinivasan Seshasai , Saghir M. Ziad 
Published: March 2018

AbstractThe objective of this paper is to study thermodiffusive flow in several ternary liquid mixtures of dodecane (nC12)‐1,2,3,4‐tetrahydronaphthalene (THN)‐isobutylbenzene (IBB) for four different compositions at normal pressure and temperature using our recently proposed modified heat exchange (mHEX) algorithm. Predictions from this algorithm are compared with the experimental data obtained in the reduced gravity environment. Comparisons have also been made with the standard heat exchange algorithm to show that the mHEX algorithm is significantly better in predicting the thermodiffusive separation.
Development and characterization of novel combinations of Ce‐Ni‐MFI solids for water gas shift reaction
Authors: Alamolhoda Sarah , Vitale Gerardo , Hassan Azfar , Nassar Nashaat N. , Pereira Almao Pedro 
Published: March 2018

AbstractIn this work, novel catalysts with different low percentages of nickel and cerium (0–3 % g/g) inside a crystalline silica framework were prepared to be tested in catalytic water gas shift reaction (WGSR) at low temperatures. The developed preparation method is distinctive as it does not require the impregnation of metals, drying, and further calcinations steps, and produces the anticipated catalysts in an efficient way. The produced solids were characterized using various characterization methods including XRD, TPR‐TPO, TPD, SEM/EDX, and N2 physisorption. Results indicated that these solids benefit from good reproducibility and ease of mass production. WGSR experiments over the produced solids at 503 K showed that Ce‐MFI solids were inactive at this temperature; however, Ni‐MFI and Ce‐Ni‐MFI solids catalyzed the reaction. At this low temperature, the catalysts containing cerium presented higher activity compared to catalysts with only nickel content. Furthermore, no methane production was observed using these catalysts.
Three different periods of CO2 dissolution into a light crude oil
Authors: Du Fengshuang , Ma Hongze , Gu Yongan 
Published: March 2018

ABSTRACTIn this paper, phase behaviours and mass‐transfer mechanisms of a Bakken light crude oil‐CO2 system are studied. A series of PVT tests of the light crude oil‐CO2 system are conducted to measure CO2 solubilities, oil‐swelling factors, and CO2‐saturated oil densities at different equilibrium pressures and the actual reservoir temperature of Tres = 56.0 °C. Five CO2 diffusion tests in the light crude oil are performed at five different initial test pressures (Pi = 4.1, 5.2, 6.3, 7.7, and 9.0 MPa) and Tres = 56.0 °C by applying the pressure decay method (PDM). The graphical method (GM) is used to analyze the measured test pressure versus time data of each diffusion test and determine CO2 average diffusivity in the light crude oil. It is found that the so‐called density‐driven natural convection can occur in the CO2‐saturated light crude oil as its measured density is much higher than that of the dead light crude oil. Three distinct periods of CO2 dissolution into the light crude oil are identified: the natural convection‐dominated period (I), the transition period, and the molecular diffusion‐dominated period (II). The determined CO2 effective diffusivities (Deff) in Period I and CO2 molecular diffusivities (D) in Period II from the GM are in the ranges of 0.28–1.75 × 10−6 m2/s and 0.87–1.94 × 10−9 m2/s at the initial test pressures of Pi = 4.1–9.0 MPa, respectively. Finally, it is also found that the constant Z‐factor approximation used in the GM may cause a relatively large error in the determination of Deff or D.
Surface treatment with amino acids of porous collagen based scaffolds to improve cell adhesion and proliferation
Authors: Rouabhia Mahmoud , Mighri Nabila , Mao Jifu , Park Hyun Jin , Mighri Frej , Ajji Abdallah , Zhang Ze 
Published: March 2018

AbstractThe purpose of this study was to improve the biocompatibility of glutaraldehyde (GA) cross‐linked chitosan coated collagen scaffold for cartilage tissue regeneration. In order to prevent the potential toxicity of GA, we treated the designed scaffold with either glutamic acid or glycine. Amino acid treated scaffolds were characterized by scanning electron microscopy (SEM) techniques. Afterward, chondrocyte interaction with the composite scaffold was investigated assessing cell adhesion and proliferation using Hoechst staining and MTT cell proliferation assay, respectively. The SEM analyses of the scaffolds’ surface and cross‐section confirmed the adhesion of amino acids on the surface of the scaffolds. We also observed that scaffolds’ porosity was reduced due to the coverage of the pores by chitosan and amino acids, leading to low porosity. The use of amino acid improved the chondrocyte adhesion and proliferation inside the scaffolds’ pores when cells were cultured onto the chitosan‐coated collagen scaffolds. Overall, our in vitro results suggest the use of amino acid to improve the biocompatibility of natural polymer composite scaffold being crosslinked with glutaraldehyde. Such scaffold has improved mechanical properties; biocompatibility thus may be useful for tissue regeneration such as cartilage.
Multiple‐Stimuli Responsive and Tunable Luminescent Supramolecular Assembly by Oligo(p‐phenylvinylene) and Surfactant
Authors: Chen Xu‐Man , Chen Yong , Liu Yu 
Published: March 2018

AbstractAchieving multicolor photoluminescence under multiple stimuli response based on a single fluorescent compound remains a great challenge. Herein, we report a novel multicolor fluorescent supramolecular assembly, which was constructed from surfactant sodium dodecyl sulfate (SLS) and fluorescent compound 1 bearing a rigid symmetrical acceptor–donor–acceptor structure. The luminescence property of 1/SLS assembly showed the multiple stimuli response towards temperature, cyclodextrin complexation and UV light irradiation, exhibiting the tunable emission wavelengths from 490 nm to 590 nm and the multicolor photoluminescence including cyan, green, yellow and orange. Furthermore, this assembly could be used in light writing owing to the fast fluorescence change within 15 s. These results could provide a convenient and useful method for fabricating smart tunable photoluminescent materials.
The “blue bottle”‐redox flow battery
Authors: Quarthal Dominik , Novotny Jana , Oetken Marco 
Published: March 2018

AbstractIm folgenden Beitrag soll eine Hybrid‐Redox‐Flow‐Batterie vorgestellt werden, in welcher eine wässrige Methylenblaulösung als Katholyt verwendet wird. Diese Batterie hat den Vorteil, dass die oxidierte/reduzierte Form des Elektrolyten durch einen eindrucksvollen Farbwechsel sichtbar gemacht werden kann. Der Aufbau unserer Hybrid‐Redox‐Flow‐Batterie ermöglicht es erstmals, dass das „Blue Bottle‐ Experiment“ auch durch einen elektrochemischen Oxidations‐ und Reduktionsvorgang in sehr kurzer Zeit durchgeführt werden kann.