Organic chemistry meets polymers, nanoscience, therapeutics and diagnostics

• Vincent M. Rotello

Beilstein J. Org. Chem. 2016, 12, 1638–1646, doi:10.3762/bjoc.12.161

• nucleic acids, where we showed that cationic nanoparticles could bind to anionic DNA and inhibit transcription [37]. We also developed a number of strategies for delivery of small molecules, including glutathione-mediated release of covalently attached thiols [38], as the effective release of drugs

Star-shaped and linear π-conjugated oligomers consisting of a tetrathienoanthracene core and multiple diketopyrrolopyrrole arms for organic solar cells

• Hideaki Komiyama,
• Chihaya Adachi and
• Takuma Yasuda

Beilstein J. Org. Chem. 2016, 12, 1459–1466, doi:10.3762/bjoc.12.142

• , including organic solar cells (OSCs) [1][2][3][4]. OSCs have drawn much attention as promising next-generation renewable energy sources because abundant sun-light energy can be directly converted into electricity. Recently, the power conversion efficiencies (PCEs) of OSCs based on small molecules with bulk

• results [32]. For most of the donor materials, including polymers and small molecules reported, the best photovoltaic performances were generally achieved with an active layer thickness of around 100 nm. However, TTA-DPP4 and TTA-DPP2 presented the highest PCEs with much thinner active layers of

Discovery of an inhibitor of the production of the Pseudomonas aeruginosa virulence factor pyocyanin in wild-type cells

• Bernardas Morkunas,
• Balint Gal,
• Warren R. J. D. Galloway,
• James T. Hodgkinson,
• Brett M. Ibbeson,
• Yaw Sing Tan,
• Martin Welch and
• David R. Spring

Beilstein J. Org. Chem. 2016, 12, 1428–1433, doi:10.3762/bjoc.12.137

• hypothesis has been validated with a number of synthetic small molecules which inhibit LasR and pyocyanin production, respectively [8][9][20][23][24][25][26]. Many such inhibitors of pyocyanin biosynthesis are based on the same general structural framework as OdDHL. For example, we have recently reported the

• ) were used (which is typically the case) [9]. Conceivably 4 could also be of value in better elucidating the role of pyocyanin in P. aeruginosa infections. Of wider significance, the identification of small molecules with antivirulence activity is needed in order to more fully evaluate the therapeutic

Selective bromochlorination of a homoallylic alcohol for the total synthesis of (−)-anverene

• Frederick J. Seidl and
• Noah Z. Burns

Beilstein J. Org. Chem. 2016, 12, 1361–1365, doi:10.3762/bjoc.12.129

• ; total synthesis; Introduction The directed enantioselective functionalization of olefins is an extremely powerful tool in synthesis. A preeminent example is the Sharpless asymmetric epoxidation (SAE), which has been featured in countless syntheses of enantioenriched small molecules [1][2]. While the

Stimuli-responsive HBPS-g-PDMAEMA and its application as nanocarrier in loading hydrophobic molecules

• Yongsheng Chen,
• Li Wang,
• Haojie Yu,
• Zain-Ul-Abdin,
• Ruoli Sun,
• Guanghui Jing,
• Rongbai Tong and
• Zheng Deng

Beilstein J. Org. Chem. 2016, 12, 939–949, doi:10.3762/bjoc.12.92

• , ionic strength and pH value) was investigated. The loading ability for small hydrophobic molecules was studied. To the best of our knowledge, this is the first report to prepare HBPS-containing stimuli-responsive materials for loading small molecules. Results and Discussion Synthesis and

Supported bifunctional thioureas as recoverable and reusable catalysts for enantioselective nitro-Michael reactions

• José M. Andrés,
• Miriam Ceballos,
• Alicia Maestro,
• Isabel Sanz and
• Rafael Pedrosa

Beilstein J. Org. Chem. 2016, 12, 628–635, doi:10.3762/bjoc.12.61

• transformations [1][2][3][4][5]. In these processes one of the major problems is related to the recovering of the catalysts. The support of the small molecules on different materials has been proposed as a solution, including their use in continuous flow processes [6][7][8][9]. The most popular supports include

Biosynthesis of α-pyrones

• Till F. Schäberle

Beilstein J. Org. Chem. 2016, 12, 571–588, doi:10.3762/bjoc.12.56

• and lactonization to yield the polyketide 76. 2.3 Biosynthesis by PKSIII systems Type III PKSs are relatively small molecules, since in contrast to the PKSs of type I and II they solely consist of a single ketosynthase. A single KS connects the CoA-bound starter and extender units; and also in this

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

• adapted to living in symbiosis with invertebrates, and have been isolated from many different parts of different insect species [12]. To further illuminate the importance of Actinobacteria as producers of valuable small molecules, we provide below additional examples of novel bioactive secondary

• in vitro analyses, but efforts should be directed towards identifying the presence and activity of candidate compounds in situ. The examination of bacterial secondary metabolisms and the respective small molecules secretome, can give insights into the up or down-regulation of (cryptic) biosynthetic

• chemical signals from microbial interactions. (1) Chemical profiling of microbial interactions using analytical techniques. (2) Dereplication leads to potentially new small molecules. (3) Optimization of the isolation protocol based on biological assessment of the activity of the isolated compounds. (4

My maize and blue brick road to physical organic chemistry in materials

• Anne J. McNeil

Beilstein J. Org. Chem. 2016, 12, 229–238, doi:10.3762/bjoc.12.24

• providing a portable and potentially inexpensive method for sensing. Considering how naïve my understanding of gelation was at the time, I am still surprised that my proposal idea worked almost exactly as described. Molecular gels form through the self-assembly of small molecules into supramolecular

A journey in bioinspired supramolecular chemistry: from molecular tweezers to small molecules that target myotonic dystrophy

• Steven C. Zimmerman

Beilstein J. Org. Chem. 2016, 12, 125–138, doi:10.3762/bjoc.12.14

• small molecules recognizing DNA mismatches has been recently published [51]. Sometimes a break can be productive and refreshing In the year or so prior to my tenure and promotion, I thought about taking on a new and seemingly more challenging problem. At that time, there was a lot of discussion and some

• design principles that lead to high affinity [50][57][58], and then to apply that knowledge to self-assembling systems. Inspired by the work of Lehn [59], Whitesides [60], and Wuest [61], Brook Duerr, Yuguo Ma, Dave Reichert, and Fanwen Zeng developed discrete cyclic assemblies of small molecules [62][63

• small molecules to treat DM2, which originates in a CCUG expansion, but Lien Nguyen, Chun-Ho Wong, and JuYeon Lee used similar rational design approaches and found lead agents that are selective for this RNA as well [89]. Although the gain of function mechanism that has CUGexp sequestering MBNL1 is well

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

• complexes hydrophobic guest species to form host–guest complexes, or inclusion compounds. The host–guest complexes formed by cyclodextrins and their hydrophobic guests, which range from small molecules to polymer substituents and sections of polymer chains, have been widely studied and utilized as building

• photo-responsive small molecules are azobenzene and its derivatives which isomerize from trans to cis and from cis to trans under irradiation with UV and visible light, respectively, and are potentially components of photo-responsive materials. In 2005, Harada et al. constructed a photo-responsive

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

• molecular-mass oligonucleotides [81], both of which involve high levels of organization in space-time. The challenge we faced was to emulate this deep-seated animal behaviour with small molecules with no organization other than to spread them out on paper [82]. Such spreading would create a graphical user

• dollars is around the total debt plus derivatives traded in the world (2013 figures). In contrast, the total world gross domestic product is only 70 trillion dollars. Emulating a bit of arts The achievement of edge detection by small molecules allowed us to apply this idea to visual arts at a rudimentary

Direct estimate of the internal π-donation to the carbene centre within N-heterocyclic carbenes and related molecules

• Diego M. Andrada,
• Nicole Holzmann,
• Thomas Hamadi and
• Gernot Frenking

Beilstein J. Org. Chem. 2015, 11, 2727–2736, doi:10.3762/bjoc.11.294

• last two decades, these versatile compounds have been widely employed in transition metal [9][10][11][12][13] and organocatalysis [14][15][16], organometallic [17][18][19] and main group synthesis [20][21][22][23][24][25][26], and activation of small molecules [27][28]. NHCs possess a divalent C(II

Learning from the unexpected in life and DNA self-assembly

• Jennifer M. Heemstra

Beilstein J. Org. Chem. 2015, 11, 2713–2720, doi:10.3762/bjoc.11.292

• , some of our greatest moments are when something doesn’t work for an unexpected reason. These “failed” experiments, while initially frustrating, have frequently led us to learn something new about the interactions of nucleic acids with each other or with ligands such as small molecules. These new

• sensors. This was surprising, as the fluorophores are small molecules attached to the termini of much larger DNA molecules. However, we found this lesson very informative, as it showed that dyes and other functional groups that we frequently append to DNA are not as innocuous as we assume them to be

• wealth of information that can be gained regarding the concentrations and flux of small molecules within these dynamic and complex environments. Additionally, the ability to fluorescently monitor targets such as small molecules inside of living cells could prove to be valuable for synthetic biology

Recent developments in copper-catalyzed radical alkylations of electron-rich π-systems

• Kirk W. Shimkin and
• Donald A. Watson

Beilstein J. Org. Chem. 2015, 11, 2278–2288, doi:10.3762/bjoc.11.248

• Kirk W. Shimkin Donald A. Watson Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, United States 10.3762/bjoc.11.248 Abstract Recently, a number of papers have emerged demonstrating copper-catalyzed alkylation reactions of electron-rich small molecules. The

Conformational equilibrium in supramolecular chemistry: Dibutyltriuret case

• Karina Mroczyńska,
• Małgorzata Kaczorowska,
• Erkki Kolehmainen,
• Ireneusz Grubecki,
• Marek Pietrzak and
• Borys Ośmiałowski

Beilstein J. Org. Chem. 2015, 11, 2105–2116, doi:10.3762/bjoc.11.227

• existence of life. It is also present in many small molecules acting as an intramolecular configurational lock. This is realized in hydrazones [1], heterocyclic urea derivatives [2], molecules exhibiting photoexcited proton transfer [3] and other compounds [4][5][6] reported also by us [7][8][9][10]. The

Recent applications of ring-rearrangement metathesis in organic synthesis

• Sambasivarao Kotha,
• Milind Meshram,
• Priti Khedkar,
• Shaibal Banerjee and
• Deepak Deodhar

Beilstein J. Org. Chem. 2015, 11, 1833–1864, doi:10.3762/bjoc.11.199

• structurally diverse small molecules starting with solid-supported phosphonate 213. In this regard, they have shown the use of a RRM protocol to prepare the bicyclic product 218 as well as tricyclic product 217. To this end, the phosphonate ester 213 reacted with a wide variety of aldehydes 214 such as aryl

Synthesis and evaluation of the biostability and cell compatibility of novel conjugates of nucleobase, peptidic epitope, and saccharide

• Dan Yuan,
• Xuewen Du,
• Junfeng Shi,
• Ning Zhou,
• Abdulgader Ahmed Baoum,
• Khalid Omar Al Footy,
• Khadija Omar Badahdah and
• Bing Xu

Beilstein J. Org. Chem. 2015, 11, 1352–1359, doi:10.3762/bjoc.11.145

• chromatography (HPLC) to purify the target conjugates. Gelation properties Supramolecular hydrogels [18][19][20][21][22][23][24] formed by self-assembly of small molecules in water, as demonstrated previously by us and other researchers, have numerous potential applications, such as encapsulation and delivery of

Thiazole-induced rigidification in substituted dithieno-tetrathiafulvalene: the effect of planarisation on charge transport properties

• Rupert G. D. Taylor,
• Joseph Cameron,
• Iain A. Wright,
• Neil Thomson,
• Olena Avramchenko,
• Alexander L. Kanibolotsky,
• Anto R. Inigo,
• Tell Tuttle and
• Peter J. Skabara

Beilstein J. Org. Chem. 2015, 11, 1148–1154, doi:10.3762/bjoc.11.129

• transistors (OFETs) Compounds 1 and 2 were used in the fabrication of bottom-gate bottom-contact OFETs to give an indication on the applicability of these small molecules to organic semiconductor devices. The use of self-assembled monolayers (SAMs) was investigated with pentafluorobenzenethiol (PFBT) and

DNA display of glycoconjugates to emulate oligomeric interactions of glycans

• Alexandre Novoa and
• Nicolas Winssinger

Beilstein J. Org. Chem. 2015, 11, 707–719, doi:10.3762/bjoc.11.81

• standard technology and customized arrays with 104–106 discrete sequences are readily available. Screening for glycan binding in a microarray format has also proven extremely valuable in glycobiology [46][47]. Based on earlier reports that small molecules [48][49] and protein microarrays [50] can be

The Shono-type electroorganic oxidation of unfunctionalised amides. Carbon–carbon bond formation via electrogenerated N-acyliminium ions

• Alan M. Jones and
• Craig E. Banks

Beilstein J. Org. Chem. 2014, 10, 3056–3072, doi:10.3762/bjoc.10.323

• been adapted to efficiently generate novel small molecules in an electrochemical microflow system [26][30]. Combining the advantages of the cation-pool method with microflow technologies has enabled the concept of “cation flow” systems (Figure 1). In this arrangement a porous carbon felt is used as an

Come-back of phenanthridine and phenanthridinium derivatives in the 21st century

• Lidija-Marija Tumir,
• Marijana Radić Stojković and
• Ivo Piantanida

Beilstein J. Org. Chem. 2014, 10, 2930–2954, doi:10.3762/bjoc.10.312

• . The common approach to complex small molecules targeting DNA and RNA usually required a number of consecutive synthetic steps, which made modification of the interesting structures a laborious and time-consuming task, quite often being the bottle-neck in the structure–activity relation research. With

• cases a switch of the binding site to the minor groove was reported. In an effort to influence DNA sequence-selective recognition by small molecules (MW <1000), our group prepared a series of phenanthridine derivatives with one or two nucleobases covalently attached at the 3 and/or 8 positions of the

• monomeric analogues) revealed significantly increased DNA-binding affinity and consequently enhanced telomerase and reverse transcriptase inhibition [69]. Conjugates of phenanthridine with other DNA and RNA active moieties Another common approach to increased selectivity of DNA- and RNA-targeting small

Removal of volatile organic compounds using amphiphilic cyclodextrin-coated polypropylene

• Ludmilla Lumholdt,
• Sophie Fourmentin,
• Thorbjørn T. Nielsen and
• Kim L. Larsen

Beilstein J. Org. Chem. 2014, 10, 2743–2750, doi:10.3762/bjoc.10.290

• , there is a great need to discover alternative methods to purify both industrial and private wastewater effectively in order to enable the EU member states to achieve the goals of the Water Framework Directive. Cyclodextrins (CDs) are cyclic, relatively small molecules consisting of units of glucose

Solution processable diketopyrrolopyrrole (DPP) cored small molecules with BODIPY end groups as novel donors for organic solar cells

• Diego Cortizo-Lacalle,
• Calvyn T. Howells,
• Upendra K. Pandey,
• Joseph Cameron,
• Neil J. Findlay,
• Anto Regis Inigo,
• Tell Tuttle,
• Peter J. Skabara and
• Ifor D. W. Samuel

Beilstein J. Org. Chem. 2014, 10, 2683–2695, doi:10.3762/bjoc.10.283

• commonly phenyl-C61-butyric acid methyl ester (PCBM), as the electron acceptor [4][5][6][7][8][9]. However, there is growing interest in the use of small molecules as donor materials in OPVs [10][11][12][13][14][15][16][17]. This interest derives from advantages and properties that small molecules show

• processing during device fabrication. The difference in power conversion efficiencies (PCEs) between polymer and small-molecule based OPVs is decreasing and PCEs over 7% have been realised in the case of the latter [18][19]. Small molecules used in OPVs are most commonly based on oligothiophenes and their

• organic field-effect transistors [24][25]. The DPP-based conjugated polymers usually show good electron and hole mobility and promising PCE values in OPVs due to large intermolecular interactions through π–π stacking. Nguyen et al. have investigated the DPP core in small molecules for OPVs with excellent

Synthesis and biological evaluation of novel N-α-haloacylated homoserine lactones as quorum sensing modulators

• Michail Syrpas,
• Ewout Ruysbergh,
• Christian V. Stevens,
• Norbert De Kimpe and
• Sven Mangelinckx

Beilstein J. Org. Chem. 2014, 10, 2539–2549, doi:10.3762/bjoc.10.265

• proximity of carbonyl groups can influence the conformation of molecules by an n→π* interaction [16][17]. Newberry and Raines, very recently proposed that tailored small molecules, that could attenuate this n→π* interaction, in which the lone pair (n) of the N-acyl oxygen overlays with the π* orbital of the