Synthesis and characterization of fluorinated azadipyrromethene complexes as acceptors for organic photovoltaics

• Forrest S. Etheridge,
• Roshan J. Fernando,
• Sandra Pejić,
• Matthias Zeller and
• Geneviève Sauvé

Beilstein J. Org. Chem. 2016, 12, 1925–1938, doi:10.3762/bjoc.12.182

• counter and pseudoreference electrodes. Crystals suitable for X-ray diffraction analysis were obtained by the slow diffusion of methanol into a dichloromethane solution. The crystals obtained were dark blue-black in appearance. Single-crystal X-ray diffraction studies were carried out using a Rigaku Rapid

Cross-linked cyclodextrin-based material for treatment of metals and organic substances present in industrial discharge waters

• Élise Euvrard,
• Nadia Morin-Crini,
• Coline Druart,
• Justine Bugnet,
• Bernard Martel,
• Cesare Cosentino,
• Virginie Moutarlier and
• Grégorio Crini

Beilstein J. Org. Chem. 2016, 12, 1826–1838, doi:10.3762/bjoc.12.172

• polymer, without an activation step, removed 20% of the total metal load in spiked solutions (SS) containing five metals at 10 mg·L−1 each. This could be attributed to surface adsorption and diffusion into the polymer network. However, it was observed that an activation step in an aqueous solution of

• precipitation and/or physical phenomena (surface adsorption, diffusion into the network and/or hydrogen bonding). This study demonstrated the efficiency of activated polyBTCA-CD to treat the inorganic load, but also to treat the organic pollutants. It can be noted that the analysis of 26 substances present in

Effect of the π-conjugation length on the properties and photovoltaic performance of A–π–D–π–A type oligothiophenes with a 4,8-bis(thienyl)benzo[1,2-b:4,5-b′]dithiophene core

• Ni Yin,
• Lilei Wang,
• Yi Lin,
• Jinduo Yi,
• Lingpeng Yan,
• Junyan Dou,
• Hai-Bo Yang,
• Xin Zhao and
• Chang-Qi Ma

Beilstein J. Org. Chem. 2016, 12, 1788–1797, doi:10.3762/bjoc.12.169

• measured. Surprisingly, 2 showed also higher device stability when compared to 3, which was mainly due to a more stable FF. More nanomophology stability was supposed to be main reason for the higher stability of the larger molecules, since larger molecules have a higher energy barrier for diffusion

3,6-Carbazole vs 2,7-carbazole: A comparative study of hole-transporting polymeric materials for inorganic–organic hybrid perovskite solar cells

• Wei Li,
• Munechika Otsuka,
• Takehito Kato,
• Yang Wang,
• Takehiko Mori and
• Tsuyoshi Michinobu

Beilstein J. Org. Chem. 2016, 12, 1401–1409, doi:10.3762/bjoc.12.134

• absorption and high carrier diffusion length as excellent features of the perovskite materials. The development of efficient hole-transporting materials (HTMs), which extract a hole from the perovskite layer and transport it to the anode, is also significant for the further improvement of the PSC

Reactivity studies of pincer bis-protic N-heterocyclic carbene complexes of platinum and palladium under basic conditions

• David C. Marelius,
• Curtis E. Moore,
• Arnold L. Rheingold and
• Douglas B. Grotjahn

Beilstein J. Org. Chem. 2016, 12, 1334–1339, doi:10.3762/bjoc.12.126

• temperature, an NMR spectrum was acquired that showed a new, unsymmetrical species, as expected for 5. Crystals were grown by vapor diffusion of pentanes into benzene and analyzed. Surprisingly, the data showed that the dimer 6-Pd had formed such that the open site was not filled with ethylene, but rather was

Synthesis of a deuterated probe for the confocal Raman microscopy imaging of squalenoyl nanomedicines

• Eric Buchy,
• Branko Vukosavljevic,
• Maike Windbergs,
• Dunja Sobot,
• Camille Dejean,
• Simona Mura,
• Patrick Couvreur and
• Didier Desmaële

Beilstein J. Org. Chem. 2016, 12, 1127–1135, doi:10.3762/bjoc.12.109

• greater anticancer activity than free gemcitabine against different experimental tumor models [7][8][9][10][11] overcoming the main drawbacks of the parent drug such as its short biological half-life and its low intracellular diffusion [12][13]. Following these initial results, the squalenoylation method

Marine-derived myxobacteria of the suborder Nannocystineae: An underexplored source of structurally intriguing and biologically active metabolites

• Antonio Dávila-Céspedes,
• Peter Hufendiek,
• Max Crüsemann,
• Till F. Schäberle and
• Gabriele M. König

Beilstein J. Org. Chem. 2016, 12, 969–984, doi:10.3762/bjoc.12.96

• metabolites and for the biosynthesis of antimicrobials [59]. In these studies, PKS genes could be amplified, sequenced and compared with known sequences in the BLAST database. The potential of producing active molecules was established by using disc diffusion antibiotic activity testing of the bacterial

Bi- and trinuclear copper(I) complexes of 1,2,3-triazole-tethered NHC ligands: synthesis, structure, and catalytic properties

• Shaojin Gu,
• Jiehao Du,
• Jingjing Huang,
• Huan Xia,
• Ling Yang,
• Weilin Xu and
• Chunxin Lu

Beilstein J. Org. Chem. 2016, 12, 863–873, doi:10.3762/bjoc.12.85

• diffusion of diethyl ether into an acetonitrile solution of the copper complex at room temperature. Green-yellow single crystals of complex 2 suitable for an X-ray diffraction study were grown from acetonitrile solution and diethyl ether. The molecular structure of complex 2 in the solid state is depicted

From steroids to aqueous supramolecular chemistry: an autobiographical career review

• Bruce C. Gibb

Beilstein J. Org. Chem. 2016, 12, 684–701, doi:10.3762/bjoc.12.69

• and the lower its translational diffusion constant, but the higher its rotational diffusion constant. Overall however, the pocket would rather be solvated: ΔGhyd ΔHhyd and TΔShyd were determined to be approximately, –5, –20, and 15 kcal mol−1 for 4 or 5 water molecules. The addition of salts to water

Creating molecular macrocycles for anion recognition

• Amar H. Flood

Beilstein J. Org. Chem. 2016, 12, 611–627, doi:10.3762/bjoc.12.60

• points after 0.5 equiv of chloride are added, which is the equivalence point for the 2:1 complex. We observe the ion pairing of the TBA+ with the 1:1 complex in the cation’s α proton (≈3 ppm), which has an inflection point at 1 equiv. Consistent with its complexation as a 1:1:1 species, the diffusion NMR

• signature for the TBA+ cation’s α proton showed a lower diffusion coefficient at 1 equiv when it forms the larger ion pair complex MC·Cl−·TBA+. Ultimately, any accurate assessment of an equilibrium constant requires inclusion of all the equilibria. There are a few tricks [25]. Some of the less stable

Interactions between 4-thiothymidine and water-soluble cyclodextrins: Evidence for supramolecular structures in aqueous solutions

• Vito Rizzi,
• Sergio Matera,
• Paola Semeraro,
• Paola Fini and
• Pinalysa Cosma

Beilstein J. Org. Chem. 2016, 12, 549–563, doi:10.3762/bjoc.12.54

• interactions are established, the diffusion of the inclusion complex from the bulk of the solution to the electrode surface is much slower than that of the guest itself leading at least to the observed current decrease (Figure 3 and Figure 4B) under our experimental conditions. As reported in [36], a decrease

• and reducing the diffusion coefficient of the molecule. The results seem to confirm the variations observed during the UV–vis measurements, in which the pyrimidine ring appeared to be involved in the interactions with CDs. It is worth mentioning that, as described in [40], our experimental data

• affecting the electron-transfer processes by changing the diffusion coefficient of the electroactive molecule by inclusion complex formation. Experiments, in the presence of glucose, mimicking the external interaction between CDs and S4TdR, were also performed with the same molar ratios of 1:1, 1:5 and 1:10

Interactions of cyclodextrins and their derivatives with toxic organophosphorus compounds

• Sophie Letort,
• Sébastien Balieu,
• William Erb,
• Géraldine Gouhier and
• François Estour

Beilstein J. Org. Chem. 2016, 12, 204–228, doi:10.3762/bjoc.12.23

• molecules may compromise their activity as poor distribution or passive diffusion across cell membranes are the usual drawbacks associated with their use. Developed after World War II, organophosphorus compounds were used as antitumor [1][2][3][4][5][6][7][8], antiviral [9][10][11][12], antihypertensive [13

Thermal and oxidative stability of Atlantic salmon oil (Salmo salar L.) and complexation with β-cyclodextrin

• Daniel I. Hădărugă,
• Mustafa Ünlüsayin,
• Alexandra T. Gruia,
• Cristina Birău (Mitroi),
• Gerlinde Rusu and
• Nicoleta G. Hădărugă

Beilstein J. Org. Chem. 2016, 12, 179–191, doi:10.3762/bjoc.12.20

• preset lower/higher temperature can be used), and the diffusion of water to the surface of the CD complex particle, which is enhanced by the possibility to control the hydrophobicity of the solvent mixture used for KFT analysis [45][46][47][48][49][50]. The total water content of 13.7 ± 0.2% for β-CD as

• agreed with the recovered yield of β-CD/ASO complexes (yield of 39.6% and 58.3% / water content of 7.3% and 9% for 1:1 molar ratio and recovery yield of 75.1% and 79.2% / water content of 8.6% and 11.6% for 3:1 molar ratio). KFT is a valuable technique for evaluating the diffusion of water molecules

• -crystallization at a 1:1 molar ratio (Table 2). The results of the KFT kinetics indicate that the diffusion of “surface” water is lower in complexes than in commercial β-CD particles and even up to ten times slower for complexes obtained at a 1:1 molar ratio. The diffusion of “strongly-retained” water in

Supramolecular structures based on regioisomers of cinnamyl-α-cyclodextrins – new media for capillary separation techniques

• Gabor Benkovics,
• Ondrej Hodek,
• Martina Havlikova,
• Zuzana Bosakova,
• Pavel Coufal,
• Milo Malanga,
• Eva Fenyvesi,
• Andras Darcsi,
• Szabolcs Beni and
• Jindrich Jindrich

Beilstein J. Org. Chem. 2016, 12, 97–109, doi:10.3762/bjoc.12.11

• intermolecular inclusion complexes: pulse field gradient spin-echo NMR experiments (PFGSE NMR) PFGSE NMR experiments were performed in order to estimate and compare the sizes of the supramolecular assemblies formed by the two regioisomers. This technique allows the quantification of the diffusion coefficient (D

• -Cin-α-CD in D2O at 25 °C recorded at various concentrations. Diffusion coefficients of 2-O-Cin-α-CD (black) and, 3-O-Cin-α-CD (red) in D2O at various concentration at 25 °C. Effect of solvent on the size distribution of aggregates formed by 2-O-Cin-α-CD at 25 °C (the applied concentrations are 10 mg

Supramolecular polymer assembly in aqueous solution arising from cyclodextrin host–guest complexation

• Jie Wang,
• Zhiqiang Qiu,
• Yiming Wang,
• Li Li,
• Xuhong Guo,
• Duc-Truc Pham,
• Stephen F. Lincoln and
• Robert K. Prud’homme

Beilstein J. Org. Chem. 2016, 12, 50–72, doi:10.3762/bjoc.12.7

• substituents alone or multiple hydrophobic substituents along the polymer backbone result in aqueous solutions with tunable viscosities, diffusion characteristics and relaxation times whilst lacking undesirable thickening effects [35][36]. The extent of such hydrophobic interaction may be controlled by either

Determination of formation constants and structural characterization of cyclodextrin inclusion complexes with two phenolic isomers: carvacrol and thymol

• Miriana Kfoury,
• David Landy,
• Steven Ruellan,
• Lizette Auezova,
• Hélène Greige-Gerges and
• Sophie Fourmentin

Beilstein J. Org. Chem. 2016, 12, 29–42, doi:10.3762/bjoc.12.5

• experiments. For the first time, a new algorithmic treatment that combines the chemical shifts and diffusion coefficients variations for all guest protons was applied to calculate Kf. The position of the hydroxy group in carvacrol and thymol did not affect the stoichiometry of the inclusion complexes but led

• structure of inclusion complexes [42]. The protons of 1 and 2 are named according to Figure 1. 1H and DOSY 1H NMR titration experiments Generally, hydrogen atoms of CD and guest are affected by the inclusion resulting in a displacement of their chemical shifts (δ) and diffusion coefficients (D). 1H and DOSY

• 1 and 2 playing the prominent role in the inclusion process and being embedded in the center of the CD cavity near to oxygen atoms. DOSY experiments also reveal the intermolecular interactions in solution by observing the variation in the intrinsic diffusion coefficients (D) of compounds upon

Bright molecules for sensing, computing and imaging: a tale of two once-troubled cities

• A. Prasanna de Silva

Beilstein J. Org. Chem. 2015, 11, 2774–2784, doi:10.3762/bjoc.11.298

• brightly fluorescent. Diffusion of H+ down the gradient at the edges allows protons to outrun the lumbering 8 and create a thin region of protonated 7 which escapes the quenching. The thinness of this bright region is determined by the diffusion coefficient of H+ in the matrix. We dry the paper carefully

• so that the diffusion coefficient of H+ is about an order of magnitude lower than that found in bulk water [85]. This procedure results in edges of 1–2 mm thickness during an experiment runtime of about 30 minutes (Figure 6). Too much or too little drying destroys the edge detection capability quite

• slightly and then erase the original photograph to leave behind the thin expansion region as the outline. This behaviour can be modelled semi-quantitatively using well-known equations of acid-base equilibria and diffusion [85]. A bit of arts The arts offer an excellent balancing influence for scientists

Synthesis of cyclic N¹-pentylinosine phosphate, a new structurally reduced cADPR analogue with calcium-mobilizing activity on PC12 cells

• Ahmed Mahal,
• Stefano D’Errico,
• Nicola Borbone,
• Brunella Pinto,
• Agnese Secondo,
• Valeria Costantino,
• Valentina Tedeschi,
• Giorgia Oliviero,
• Vincenzo Piccialli and
• Gennaro Piccialli

Beilstein J. Org. Chem. 2015, 11, 2689–2695, doi:10.3762/bjoc.11.289

• results indicate that 3 and 4 possess almost the same activity, thus indicating that the role of the pyrophosphate bridge is not stringent and that the introduction of an alkyl chain in the N1 position of the purine base improves the permeation of the cell membrane by passive diffusion or through an

Biocatalysis for the application of CO₂ as a chemical feedstock

• Apostolos Alissandratos and
• Christopher J. Easton

Beilstein J. Org. Chem. 2015, 11, 2370–2387, doi:10.3762/bjoc.11.259

• , the archetypal super-enzyme for which catalytic rates reach the limits of diffusion [30][31]. CO2 consumed by enzymes is therefore efficiently replenished through rapid HCO3− dehydration (Figure 2). Living organisms have developed various mechanisms to increase the effective concentration of CO2

• enzymes used. The application of enzymes within whole-cells allows their production and utilisation with minimal processing and circumvents biocatalyst purification, though in this case there are limitations related to substrate/product diffusion and background metabolic activity. The optimal approach in

• each case, as for any multi-enzymatic synthesis, will depend on a combination of factors such as the number of enzymes to be utilised, the ease of substrate and product diffusion through the cell membrane, and the presence of unwanted background reactions. Within a well-understood cellular chassis, the

Preparation of Pickering emulsions through interfacial adsorption by soft cyclodextrin nanogels

• Shintaro Kawano,
• Toshiyuki Kida,
• Mitsuru Akashi,
• Hirofumi Sato,
• Motohiro Shizuma and
• Daisuke Ono

Beilstein J. Org. Chem. 2015, 11, 2355–2364, doi:10.3762/bjoc.11.257

• Information File 1. Dynamic light scattering (DLS) The particle size distribution was measured at 25 °C using DLS6000HL (Otsuka Electronic Co.) equipped with a He-Ne laser (wavelength 632.8 nm). The mean particle diameter was calculated from the diffusion coefficients using the Stokes–Einstein equation. The

Half-sandwich nickel(II) complexes bearing 1,3-di(cycloalkyl)imidazol-2-ylidene ligands

• Johnathon Yau,
• Kaarel E. Hunt,
• Laura McDougall,
• Alan R. Kennedy and
• David J. Nelson

Beilstein J. Org. Chem. 2015, 11, 2171–2178, doi:10.3762/bjoc.11.235

• , elemental analysis and X-ray crystallography (Figure 1). Selected crystallographic data can be found in Table 1, and some key bond lengths in Table 2. X-ray quality crystals were obtained by slow diffusion of pentane into a DCM solution of each complex. The 1H NMR spectra show the expected features; a sharp

Ru complexes of Hoveyda–Grubbs type immobilized on lamellar zeolites: activity in olefin metathesis reactions

• Hynek Balcar,
• Naděžda Žilková,
• Martin Kubů,
• Michal Mazur,
• Zdeněk Bastl and
• Jiří Čejka

Beilstein J. Org. Chem. 2015, 11, 2087–2096, doi:10.3762/bjoc.11.225

• ), with large BET areas and pore volumes, proved to be very suitable supports, due to easy attachment of bulky organometallic complexes onto silica surface ensuring rapid diffusion of reactants to the active catalytic sites [5][6][7][8][9][10][11][12]. Several strategies of immobilization have been

• -metathesis, in accord with the characters of both reactants (classes of reactants in CM according to Grubbs [35]). The data presented indicated that the depressed activity of HGIIN+Cl−/MCM-22 in the self-metathesis of methyl oleate was not connected with a slow diffusion of the reactant to the active centers

The marine sponge Agelas citrina as a source of the new pyrrole–imidazole alkaloids citrinamines A–D and N-methylagelongine

• Christine Cychon,
• Ellen Lichte and
• Matthias Köck

Beilstein J. Org. Chem. 2015, 11, 2029–2037, doi:10.3762/bjoc.11.220

• cytotoxic activity. Classical agar diffusion assays were performed using the fungus Aspergillus niger, the yeast Saccharomyces cerevisiae as well as the Gram-negative bacterium Escherichia coli, and the Gram-positive bacterium Micrococcus luteus and Mycobacterium phlei as test organisms. In agar diffusion

• . Antimicrobial assay As already described in [18] the antimicrobial activities were determined by agar diffusion tests using paper disks of 6 mm diameter soaked with 20 µL of the test compound in MeOH (1 mg/mL). The microorganisms were obtained from the HZI collection, grown on standard media, and cultured in

Investigation of the role of stereoelectronic effects in the conformation of piperidones by NMR spectroscopy and X-ray diffraction

• Cesar Garcias-Morales,
• David Ortegón-Reyna and
• Armando Ariza-Castolo

Beilstein J. Org. Chem. 2015, 11, 1973–1984, doi:10.3762/bjoc.11.213

• the 6-311++G(d,p) basis set. This basis set includes diffusion and polarization functions, and performs better for the description of molecular orbitals from geometry optimization and NBO analysis. General procedure for the synthesis of 2,4-diphenyl-3-azabicyclo[3.3.1]nonan-9-ones The compounds 1–2

Hexacoordinate Ru-based olefin metathesis catalysts with pH-responsive N-heterocyclic carbene (NHC) and N-donor ligands for ROMP reactions in non-aqueous, aqueous and emulsion conditions

• Shawna L. Balof,
• K. Owen Nix,
• Matthew S. Olliff,
• Sarah E. Roessler,
• Arpita Saha,
• Kevin B. Müller,
• Ulrich Behrens,
• Edward J. Valente and
• Hans-Jörg Schanz

Beilstein J. Org. Chem. 2015, 11, 1960–1972, doi:10.3762/bjoc.11.212

• complex 12 suitable for X-ray diffraction were obtained via layer diffusion of heptane into a concentrated THF solution (Figure 2). Hexacoordinated complex 12 adopts the expected distorted octahedral coordination sphere around the Ru center with trans chloride and cis DMAP ligands. In comparison to

• ; N, 12.41; found: C, 58.26; H, 6.49, N, 11.74. Crystal structure determination of complex 12. Crystals suitable for X-ray diffraction were obtained by layer diffusion of heptane into a THF solution of complex 12 at ambient temperatures over a period of 3 d to yield dark brown prisms. The crystals do