Synthesis of medronic acid monoesters and their purification by high-performance countercurrent chromatography or by hydroxyapatite

• Elina Puljula,
• Jouko Vepsäläinen and
• Petri A. Turhanen

Beilstein J. Org. Chem. 2016, 12, 2145–2149, doi:10.3762/bjoc.12.204

• : bisphosphonate; bisphosphonate monoester; high performance counter current chromatography; hydroxyapatite; medronic acid; Introduction Bisphosphonates (BPs) have been used for decades in the treatment of bone-related diseases as well as for bone imaging. Nevertheless, several recent reports have demonstrated

Economical and scalable synthesis of 6-amino-2-cyanobenzothiazole

• Jacob R. Hauser,
• Hester A. Beard,
• Mary E. Bayana,
• Katherine E. Jolley,
• Stuart L. Warriner and
• Robin S. Bon

Beilstein J. Org. Chem. 2016, 12, 2019–2025, doi:10.3762/bjoc.12.189

• Laboratories, University of Leeds, Leeds LS2 9JT, UK 10.3762/bjoc.12.189 Abstract 2-Cyanobenzothiazoles (CBTs) are useful building blocks for: 1) luciferin derivatives for bioluminescent imaging; and 2) handles for bioorthogonal ligations. A particularly versatile CBT is 6-amino-2-cyanobenzothiazole (ACBT

• -cyanobenzothiazoles; DABCO; luciferins; organocatalysis; Introduction Functionalised 2-cyanobenzothiazoles (CBTs, 1) are key building blocks for the synthesis of luciferins 3 [1][2][3], substrates of natural and engineered firefly luciferases that are widely used for bioluminescence imaging (BLI) [4][5]. The typical

• bioorthogonal ligation and bioluminescent imaging. The procedure allowed the safe synthesis of 8 at multigram scale and in high purity. In addition, the sole use of filtrations and crystallisations for purification of all intermediates and products, in combination with the endothermic nature of the controlled

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

• chelation [1][2][3][4]. BF2+-chelated ADP derivatives (Figure 1b) in particular have drawn interest for photodynamic therapy, bio-imaging and light harvesting applications [5][6][7][8]. We have shown that derivatives of Zn(ADP)2 are promising electron acceptors for organic photovoltaics (OPVs) [9][10]. A

Ionic liquids as transesterification catalysts: applications for the synthesis of linear and cyclic organic carbonates

• Maurizio Selva,
• Alvise Perosa,
• Sandro Guidi and
• Lisa Cattelan

Beilstein J. Org. Chem. 2016, 12, 1911–1924, doi:10.3762/bjoc.12.181

• therapeutics, imaging agents and packaging films and coatings [77]. Conclusion The literature survey illustrated in this review highlights three main facts. Firstly, organocatalysis by ionic liquids can be an efficient tool for base and even acid-catalyzed transesterification reactions in place of traditional

Synthesis and properties of fluorescent 4′-azulenyl-functionalized 2,2′:6′,2″-terpyridines

• Adrian E. Ion,
• Liliana Cristian,
• Mariana Voicescu,
• Masroor Bangesh,
• Augustin M. Madalan,
• Daniela Bala,
• Constantin Mihailciuc and
• Simona Nica

Beilstein J. Org. Chem. 2016, 12, 1812–1825, doi:10.3762/bjoc.12.171

• have been investigated for their potential applications in catalysis, photovoltaic cells and biomedical science [5]. Special attention has been paid to fluorescence responses of metal–terpyridine compounds permitting access to new sensors for bioassays and in vivo imaging purposes [6]. The

Dinuclear thiazolylidene copper complex as highly active catalyst for azid–alkyne cycloadditions

• Anne L. Schöffler,
• Ata Makarem,
• Frank Rominger and
• Bernd F. Straub

Beilstein J. Org. Chem. 2016, 12, 1566–1572, doi:10.3762/bjoc.12.151

• bioactive surfaces [8][14], imaging of biochemical processes [15], localization of bioactive compounds inside living cells [16], syntheses of small-molecule screening libraries [17], catenane and rotaxane syntheses [18], in reactions under continuous flow processing [19], polymer and surface science [20][21

Towards potential nanoparticle contrast agents: Synthesis of new functionalized PEG bisphosphonates

• Souad Kachbi-Khelfallah,
• Maelle Monteil,
• Margery Cortes-Clerget,
• Evelyne Migianu-Griffoni,
• Jean-Luc Pirat,
• Olivier Gager,
• Julia Deschamp and
• Marc Lecouvey

Beilstein J. Org. Chem. 2016, 12, 1366–1371, doi:10.3762/bjoc.12.130

• for biomedical imaging applications, the adsorption of plasmatic proteins on the surface of nanoparticles must be prevented to reduce the hepatic capture and increase the plasmatic time life. In biologic media, metal oxide nanoparticles are not stable and must be coated by biocompatible organic

• the development of superparamagnetic iron oxide nanoparticles (SPIONPs) because of their biocompatibility which allows there in vivo use both for diagnosis in magnetic resonance imaging and in therapy [1][2]. Most often, it is necessary to modify the surface of SPIONPs to increase the metabolic

Application of Cu(I)-catalyzed azide–alkyne cycloaddition for the design and synthesis of sequence specific probes targeting double-stranded DNA

• Svetlana V. Vasilyeva,
• Vyacheslav V. Filichev and
• Alexandre S. Boutorine

Beilstein J. Org. Chem. 2016, 12, 1348–1360, doi:10.3762/bjoc.12.128

• , so they were successfully used for both gene expression regulation and the synthesis of fluorescent probes for DNA imaging in fixed and live cells [1][2][3][8][9]. However, the length of the sequence recognized by the classical hairpin polyamides (5–6 base pairs) is much shorter than that for TFOs

Synthesis, fluorescence properties and the promising cytotoxicity of pyrene–derived aminophosphonates

• Jarosław Lewkowski,
• Maria Rodriguez Moya,
• Anna Wrona-Piotrowicz,
• Janusz Zakrzewski,
• Renata Kontek and
• Gabriela Gajek

Beilstein J. Org. Chem. 2016, 12, 1229–1235, doi:10.3762/bjoc.12.117

• biological imaging. Investigation of cytotoxic effects of studied compounds The cytotoxic effects of dimethyl aminophosphonates 3Aa, 3Ab, 3Ac, 3Ad, 3Ai and dimethyl [hydroxy(pyren-1-yl)methyl]phosphonate (5A) were investigated with two human colorectal carcinoma cell lines: HT29 and HCT116 and also on the

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

• fulfill this task, radioactive labeling or fluorescent probes have been thoroughly used. For example, the subcellular localization of the 3H-radiolabeled GemSQ conjugate has been evaluated by micro-autoradiography coupled to confocal imaging of fluorescently labeled cellular structures [21]. A dual

• , its coupling with gemcitabine and the Raman spectra of the deuterated GemSQ nanoassemblies, opening the way to perform intracellular imaging of squalenoyl nanomedicine (Figure 1). Results and Discussion Chemical synthesis of squalenic acid-d6 and GemSQ-d6 conjugate In a first approach we decided to

Creating molecular macrocycles for anion recognition

• Amar H. Flood

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

• microscopy (STM) imaging. Their shape persistence makes them ideal for the study of structure–property relationships to enable deep understanding of anion recognition phenomena. The identification of 1,2,3-triazoles as linkers, ligands and building blocks. The synthetic creation of macrocycles sets the scene

• self-assembly and anion binding (Figure 17a) using STM and were surprised by what we saw. Clear in the imaging (Figure 17b) were their shapes, looking like lumpy donuts; a shape similar to the one offered by Japan’s Mister Donut. Interestingly, these macrocycles displayed a reliable propensity for

Self and directed assembly: people and molecules

• Tony D. James

Beilstein J. Org. Chem. 2016, 12, 391–405, doi:10.3762/bjoc.12.42

• will develop as a direct result of the increased importance of animal, tissue and cellular imaging techniques using boronic acid receptors [124]. “Education is the passport to the future, for tomorrow belongs to those who prepare for it today.” – Malcolm X (1925–1965) Author biography Tony D. James is

Art, auto-mechanics, and supramolecular chemistry. A merging of hobbies and career

• Eric V. Anslyn

Beilstein J. Org. Chem. 2016, 12, 362–376, doi:10.3762/bjoc.12.40

• -based differential sensing is likewise struggling for a solid foothold in the economy. In contrast, imaging agents are clearly a frontier. These are the kinds of sensors that Tony Czarnik originally envisioned [72], and commercial success has been achieved with the company Life Technologies, formally

Diastereoselective synthesis of new O-alkylated and C-branched inositols and their corresponding fluoro analogues

• Charlotte Collet,
• Françoise Chrétien,
• Yves Chapleur and
• Sandrine Lamandé-Langle

Beilstein J. Org. Chem. 2016, 12, 353–361, doi:10.3762/bjoc.12.39

• derivatives, bearing an arm terminated either with a hydroxy group or a fluorine atom, could be interesting candidates for diastereoisomeric intermediates and biological evaluations, especially for PET imaging experiments. Keywords: C-branched; diastereoselective; fluoroinositols; inositols; O-alkylated

• this compound crosses the blood brain barrier (BBB) with difficulty [32]. The same PET imaging studies using the diastereoisomeric compound of myo configuration (2-[18F]fluoro-2-deoxy-myo-inositol), did not get better results [33]. On the other hand, these radiotracers have shown interesting features

• in the diagnosis of breast cancer with this imaging technique [33][34]. Considering the synthetic and biological importance of inositol analogues, the design of new inositol derivatives to study their biological properties and to understand their binding mechanisms with molecular targets, for

Natural products from microbes associated with insects

• Christine Beemelmanns,
• Huijuan Guo,
• Maja Rischer and
• Michael Poulsen

Beilstein J. Org. Chem. 2016, 12, 314–327, doi:10.3762/bjoc.12.34

• identified as piericidin derivatives (e.g., piericidin A1 (1), Figure 3) and the chlorinated indole derivative streptochlorin (2). Imaging analysis based on a combination of laser desorption/ionization (LDI)–time of flight (TOF) mass spectrometry imaging visualized the spatial distribution of the antibiotics

• pathways. This in turn can lead to the discovery of new metabolic pathways that would otherwise be silent or undetected under typical laboratory cultivation conditions. In recent years many successful analytical methods including UHPLC–DAD and UHPLC–MS-based techniques, imaging mass spectrometry (IMS) [138

Enabling technologies and green processes in cyclodextrin chemistry

• Giancarlo Cravotto,
• Marina Caporaso,
• Laszlo Jicsinszky and
• Katia Martina

Beilstein J. Org. Chem. 2016, 12, 278–294, doi:10.3762/bjoc.12.30

• -soluble cyanine/β-CD derivatives have been efficiently prepared via CuAAC under simultaneous US/MW irradiation at 75 °C for 2 h (MW 15 W and US 20 W) in good yields (23% and 33%). These dyes were used as versatile carriers for drug delivery and optical imaging. Preparation of CD-grafted materials and CD

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

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

• ) equipped with a FLUAR 40X oil objective lens. The experiments employed a digital imaging system composed of a MicroMax 512BFT cooled CCD camera (Princeton Instruments, Trenton, NJ, USA), LAMBDA 10-2 filter wheeler (Sutter Instruments, Novato, CA, USA), and Meta-Morph/MetaFluor Imaging System software

• (Universal Imaging, West Chester, PA, USA). After loading, the cells were illuminated alternately at 340 and 380 nm by a Xenon lamp. The emitted light was passed through a 512 nm barrier filter. Fura-2AM fluorescence intensity was measured every 3 s. Forty to sixty-five individual cells were selected and

Carbon–carbon bond cleavage for Cu-mediated aromatic trifluoromethylations and pentafluoroethylations

• Tsuyuka Sugiishi,
• Hideki Amii,
• Kohsuke Aikawa and
• Koichi Mikami

Beilstein J. Org. Chem. 2015, 11, 2661–2670, doi:10.3762/bjoc.11.286

• PET imaging. The reason is that the [18F] isotope has a longer half-life (110 min) than 13N (10 min) or 15O (2 min); however, the incorporation of [18F] must be rapid and the use of the products containing [18F] must be immediate. Many of the reported strategies have a limited scope of starting

• materials or require expensive reagents and a multistep synthesis. The [18F]trifluoromethylation performed with commercially available reagents by using [18F]fluoride demands no complex such as [18F]CF2Cu, and thus the method should contribute to efficient PET imaging [42] (Scheme 8). Synthesis of

Inclusion complexes of 2-methoxyestradiol with dimethylated and permethylated β-cyclodextrins: models for cyclodextrin–steroid interaction

• Mino R. Caira,
• Susan A. Bourne,
• Halima Samsodien and
• Vincent J. Smith

Beilstein J. Org. Chem. 2015, 11, 2616–2630, doi:10.3762/bjoc.11.281

• Nikon SMZ-10 stereoscopic microscope. The Soft Imaging system, analySIS [31] was used to process the images. For TGA a Mettler Toledo TGA/SDTA851e instrument was employed with a nitrogen gas purge (flow rate 30 cm3/min). Indium (mp 156.6 °C) and aluminium (mp 660.3 °C) were used for all calibrations

Smart molecules for imaging, sensing and health (SMITH)

• Bradley D. Smith

Beilstein J. Org. Chem. 2015, 11, 2540–2548, doi:10.3762/bjoc.11.274

• imaging, ion-pair receptors, rotaxane synthesis, squaraine rotaxanes, and synthtavidin technology. The article concludes with a short perspective of likely future directions in biomedical supramolecular chemistry. Keywords: fluorescence; ion-pair receptors; membrane transport; molecular imaging; rotaxane

• phosphatidylserine appear on the surface of cells and induce subsequent secondary biological signaling processes such as blood clotting and cell clearance by macrophages [8]. Molecular imaging Our work on synthetic phospholipid scramblases required us to develop methods for quantifying phospholipid levels on the

• on the cell surface during the process of apoptosis or programmed cell death. Thus, phosphatidylserine is an excellent biomarker of cell death and an attractive target for molecular imaging. We reasoned that synthetic anion receptors such as zinc dipicolylamine (ZnDPA) coordination complexes would

Size-controlled and redox-responsive supramolecular nanoparticles

• Raquel Mejia-Ariza,
• Gavin A. Kronig and
• Jurriaan Huskens

Beilstein J. Org. Chem. 2015, 11, 2388–2399, doi:10.3762/bjoc.11.260

• applications owing to control over their size, their assembly/disassembly, and the modular character for the versatile incorporation of agents aiming for imaging [3], photothermal therapy [4], drug delivery [5][6][7] and gene delivery [8][9][10] applications. Different approaches have been used to form SNPs

• fruitful discussions and Mark A. Smithers for HR-SEM imaging.

Syntheses of 2-substituted 1-amino-4-bromoanthraquinones (bromaminic acid analogues) – precursors for dyes and drugs

• Enas M. Malik,
• Younis Baqi and
• Christa E. Müller

Beilstein J. Org. Chem. 2015, 11, 2326–2333, doi:10.3762/bjoc.11.253

• synthetic AQs, are utilized for a wide range of applications, e.g., in textile industry [7][8], paints, foods, cosmetics, pharmaceuticals, and imaging devices [3][9][10][11][12][13], and there is a continuous interest in optimizing this class of compounds as documented in recent literature [14][15][16][17

Easy access to heterobimetallic complexes for medical imaging applications via microwave-enhanced cycloaddition

• Nicolas Desbois,
• Sandrine Pacquelet,
• Adrien Dubois,
• Clément Michelin and
• Claude P. Gros

Beilstein J. Org. Chem. 2015, 11, 2202–2208, doi:10.3762/bjoc.11.239

• easily prepared as potential MRI/PET (SPECT) bimodal contrast agents incorporating one metal (Mn, Gd) for the enhancement of contrast for MRI applications and one “cold” metal (Cu, Ga, In) for future radionuclear imaging applications. Preliminary relaxivity measurements showed that the reported complexes

• are promising contrast agents (CA) in MRI. Keywords: click chemistry; corrole; DOTA; microwave; NOTA; porphyrin; Introduction Magnetic resonance imaging (MRI), positron emission tomography (PET) or single photon emission computed tomography (SPECT) are actually the most commonly used imaging

• modalities. MRI provides high-resolution (at the submillimeter level), but is limited by its low sensitivity. Conversely, PET and SPECT imaging are more sensitive methods but they both suffer from low anatomical resolution. As one single modality is usually not sufficient to obtain all the necessary

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

• contains a molecule of cocrystallized water. The hydrogen atoms of the water molecule were omitted from the structure due to thermal uncertainty. AFM image produced from COE/DCPD latex film. Measurement: AFM tapping at room temperature, material contrast using Phase Imaging. Synthesis of 2nd Grubbs-type