- Synthesis and Preliminary PET Imaging Studies of a FAAH Radiotracer ([11C]MPPO) Based on α-Ketoheterocyclic Scaffold
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Fatty acid amide hydrolase (FAAH) is one of the principle enzymes for metabolizing endogenous cannabinoid neurotransmitters such as anandamide, and thus regulates endocannabinoid (eCB) signaling. Selective pharmacological blockade of FAAH has emerged as a potential therapy to discern the endogenous functions of anandamide-mediated eCB pathways in anxiety, pain, and addiction. Quantification of FAAH in the living brain by positron emission tomography (PET) would help our understanding of the endocannabinoid system in these conditions. While most FAAH radiotracers operate by an irreversible ("suicide") binding mechanism, a FAAH tracer with reversibility would facilitate quantitative analysis. We have identified and radiolabeled a reversible FAAH inhibitor, 7-(2-[11C]methoxyphenyl)-1-(5-(pyridin-2-yl)oxazol-2-yl)heptan-1-one ([11C]MPPO) in 13% radiochemical yield (nondecay corrected) with >99% radiochemical purity and 2 Ci/μmol (74 GBq/μmol) specific activity. The tracer showed moderate brain uptake (0.8 SUV) with heterogeneous brain distribution. However, blocking studies with a potent FAAH inhibitor URB597 demonstrated a low to modest specificity to the target. Measurement of lipophilicity, metabolite, and efflux pathway analysis were also performed to study the pharmacokinetic profile of [11C]MPPO. In all, we reported an efficient radiolabeling and preliminary evaluation of the first-in-class FAAH inhibitor [11C]MPPO with α-ketoheterocyclic scaffold. (Chemical Equation Presented).
- Wang, Lu,Yui, Joji,Wang, Qifan,Zhang, Yiding,Mori, Wakana,Shimoda, Yoko,Fujinaga, Masayuki,Kumata, Katsushi,Yamasaki, Tomoteru,Hatori, Akiko,Rotstein, Benjamin H.,Collier, Thomas Lee,Ran, Chongzhao,Vasdev, Neil,Zhang, Ming-Rong,Liang, Steven H.
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Read Online
- Synthesis of Oct-1-ene
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Oct-1-ene, with 98percent and 93percent deuterium incorporation at C-2 and C-8, respectively, is prepared from 6-bromohexan-1-ol in a six-step synthesis which offers access to a wide range of ω-labelled acyclic aliphatic compounds.
- Read, Gordon,Townsend, Ian
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Read Online
- The synthesis of 14-membered macrocyclic ethers
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As part of an ongoing study of the chemistry of macrocyclic compounds, 14-membered macrocyclic ethers with a variety of methyl substitution patterns were synthesized. The preparation of these macrocyclic ethers involved either the Baeyer-Villiger ring expansion of a cyclic ketone, or the macrolactonization of a hydroxy acid to give a lactone. The lactone carbonyl was removed either by conversion to an intermediate thionolactone obtained by reaction with Lawesson's reagent and reduction, or by direct reduction using a boron trifluoride etherate mediated sodium borohydride reaction.
- Clyne, Dean S.,Weiler, Larry
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Read Online
- Modular Assembly of Vibrationally and Electronically Coupled Rhenium Bipyridine Carbonyl Complexes on Silicon
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Hybrid inorganic/organic heterointerfaces are promising systems for next-generation photocatalytic, photovoltaic, and chemical-sensing applications. Their performance relies strongly on the development of robust and reliable surface passivation and functionalization protocols with (sub)molecular control. The structure, stability, and chemistry of the semiconductor surface determine the functionality of the hybrid assembly. Generally, these modification schemes have to be laboriously developed to satisfy the specific chemical demands of the semiconductor surface. The implementation of a chemically independent, yet highly selective, standardized surface functionalization scheme, compatible with nanoelectronic device fabrication, is of utmost technological relevance. Here, we introduce a modular surface assembly (MSA) approach that allows the covalent anchoring of molecular transition-metal complexes with sub-nanometer precision on any solid material by combining atomic layer deposition (ALD) and selectively self-assembled monolayers of phosphonic acids. ALD, as an essential tool in semiconductor device fabrication, is used to grow conformal aluminum oxide activation coatings, down to sub-nanometer thicknesses, on silicon surfaces to enable a selective step-by-step layer assembly of rhenium(I) bipyridine tricarbonyl molecular complexes. The modular surface assembly of molecular complexes generates precisely structured spatial ensembles with strong intermolecular vibrational and electronic coupling, as demonstrated by infrared spectroscopy, photoluminescence, and X-ray photoelectron spectroscopy analysis. The structure of the MSA can be chosen to avoid electronic interactions with the semiconductor substrate to exclusively investigate the electronic interactions between the surface-immobilized molecular complexes.
- Allegretti, Francesco,Amati, Matteo,Barth, Johannes V.,Bartl, Johannes D.,Bondino, Federica,Cattani-Scholz, Anna,Deimel, Peter S.,Gregoratti, Luca,Henning, Alex,Magnano, Elena,Nickel, Bert,Ober, Martina F.,Ochsenfeld, Christian,Paulus, Claudia,Rieger, Bernhard,Savasci, G?kcen,Sharp, Ian D.,Stutzmann, Martin,Thomas, Christopher,Yazdanshenas, Bahar,Zeller, Patrick
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supporting information
p. 19505 - 19516
(2021/11/26)
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- Synthesis and Cytotoxicity of 1,4-Naphthoquinone Oxime Derivatives
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A series of hydroxylated 1,4-naphthoquinone oximes were designed and synthesized. The in vitro cytotoxicity of these compounds was evaluated against five human cancer cell lines and human skin fibroblast cell line. Among them, compounds (1E,4E)-6-{1-[(5-Hydroxypentyl)oxy]-2,2-dimethylbut-3-en-1-yl}-5,8- dimethoxynaphthalene-1,4-dione dioxime and (1E,4E)-6-{1-[(6-Hydroxyhexyl)oxy]-2,2-dimethylbut-3-en-1-yl}-5,8-dimethoxynaphthalene-1,4-dione dioxime displayed higher cytotoxicity in three cancer cell lines than the positive drug 5-fluorouracil.
- Zhang,Dong,Meng,Huang,Li
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p. 2388 - 2393
(2019/01/04)
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- A (Z, Z, E) - 7, 11, 13 - sixteen carbon three activated olefinic ketones synthesis method (by machine translation)
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The invention relates to an improved synthetic method of (Z,Z,E)-7,11,13-hexadecatrienal, wherein the (Z,Z,E)-7,11,13-hexadecatrienal is an important component in a sex pheromone compound of phyllocnistis citrella. The improved synthetic method is carried out with 6-bromo-1-hexanol as an initial raw material and through a coupled reaction, a Wittig reaction and other reactions to synthesize the (Z,Z,E)-7,11,13-hexadecatrienal. The improved synthetic method is advantaged in that the raw material is low in cost and easy to get, and the reactions are safe and convenient in operations and is short in step periods. The improved synthetic method is high in product yield, is free of environmental pollution and can achieve better economic benefit.
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Page/Page column 2; 3; 8; 11
(2018/07/15)
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- Donepezil–melatonin hybrids as butyrylcholinesterase inhibitors: Improving binding affinity through varying mode of linking fragments
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Hybrid inhibitors of acetyl- and butyrylcholinesterase are compounds that combine structural motifs of two different classical inhibitors, leading to a dual binding ligand. A rapidly growing collection of those compounds involves a wide diversity of structural motifs, but the way of linking two active fragments and its impact on the affinity toward cholinesterases usually remains beyond the extent of investigation. We present hereby a detailed analysis of this aspect using melatonin–donepezil hybrids. A new series of compounds, in which two fragments are connected using a carbamate linker, exhibits excellent activity and selectivity toward butyrylcholinesterase.
- ?ozińska, Iwona,?wierczyńska, Aleksandra,Mol?da, Zuzanna,Hartman, Alwin M.,Hirsch, Anna K. H.,Czarnocki, Zbigniew
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- Method for synthesizing (E)-7-dodecen-1-ol acetate
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The invention belongs to the technical field of insect pheromone synthesis, and discloses a novel method for synthesizing (E)-7-dodecen-1-ol acetate. The method comprises the following steps: reactinga starting raw material 6-bromo-1-hexanol with 2,3-dihydropyran to obtain 1-tetrahydropyranyloxy-6-bromohexane, and carrying out a coupling reaction on the 1-tetrahydropyranyloxy-6-bromohexane and 1-hexyne in the presence of n-butyllithium to generate 1-tetrahydropyranyloxy-7-dodecyne; reducing the 1-tetrahydropyranyloxy-7-dodecyne by lithium aluminum hydroxide in diethylene glycol dimethyl etherto obtain (E)-tetrahydropyranyloxy-7-dodecene; and removing tetrahydropyran protecting groups by using p-toluenesulfonic acid to synthesize (E)-7-dodecen-1-ol acetate, and finally reacting the (E)-7-dodecen-1-ol acetate with acetyl chloride to obtain the target product (E)-7-dodecen-1-ol acetate. The method has the advantages of simple synthesis route, mild reaction conditions, and realization ofthe total yield reaching 49%.
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Paragraph 0011; 0023-0025
(2019/01/08)
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- The molecular structure of thio-ether fatty acids influences PPAR-dependent regulation of lipid metabolism
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Thio-ether fatty acids (THEFAs), including the parent 2-(tetradecylthio)acetic acid (TTA), are modified fatty acids (FAs) that have profound effects on lipid metabolism given that they are blocked for β-oxidation, and able to act as peroxisome proliferator-activated receptor (PPAR) agonists. Therefore, TTA in particular has been tested clinically for its therapeutic potential against metabolic syndrome related disorders. Here, we describe the preparation of THEFAs based on the TTA scaffold with either a double or a triple bond. These are tested in cultured human skeletal muscle cells (myotubes), either as free acid or following esterification as phospholipids, lysophospholipids or monoacylglycerols. Metabolic effects are assessed in terms of cellular bioavailabilities in myotubes, by FA substrate uptake and oxidation studies, and gene regulation studies with selected PPAR-regulated genes. We note that the inclusion of a triple bond promotes THEFA-mediated FA oxidation. Furthermore, esterification of THEFAs as lysophospholipids also promotes FA oxidation effects. Given that the apparent clinical benefits of TTA administration were offset by dose limitation and poor bioavailability, we discuss the possibility that a selection of our latest THEFAs and THEFA-containing lipids might be able to fulfill the therapeutic potential of the parent TTA while minimizing required doses for efficacy, side-effects and adverse reactions.
- Lund, Jenny,Stensrud, Camilla,Rajender,Bohov, Pavol,Thoresen, G. Hege,Berge, Rolf K.,Wright, Michael,Kamal, Ahmed,Rustan, Arild C.,Miller, Andrew D.,Skorve, Jon
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p. 1191 - 1203
(2016/03/01)
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- Identification of β-hydroxy fatty acid esters and primary, secondary-alkanediol esters in cuticular waxes of the moss Funaria hygrometrica
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The plant cuticle, a multi-layered membrane that covers plant aerial surfaces to prevent desiccation, consists of the structural polymer cutin and surface-sealing waxes. Cuticular waxes are complex mixtures of ubiquitous, typically monofunctional fatty acid derivatives and taxon-specific, frequently bifunctional specialty compounds. To further our understanding of the chemical diversity of specialty compounds, the waxes on the aerial structures of the leafy gametophyte, sporophyte capsule, and calyptra of the moss Funaria hygrometrica were surveyed. Respective moss surfaces were extracted, and resulting lipid mixtures were analyzed by gas chromatography-mass spectrometry (GC-MS). The extracts contained ubiquitous wax compound classes along with two prominent, unidentified classes of compounds that exhibited some characteristics of bifunctional structures. Microscale transformations led to derivatives with characteristic MS fragmentation patterns suggesting possible structures for these compounds. To confirm the tentative structure assignments, one compound in each of the suspected homologous series was synthesized. Based on GC-MS comparison with the authentic standards, the first series of compounds was identified as containing esters formed by β-hydroxy fatty acids and wax alcohols, with ester chain lengths varying from C42 to C50 and the most prominent homolog being C46. The second series consisted of fatty acid esters of 1,7-alkanediols, linked via the primary hydroxyl group, with ester chain lengths C40-C52 also dominated by the C46 homolog. The β-hydroxy acid esters were restricted to the sporophyte capsule, and the diol esters to the leafy gametophyte and calyptra. Based on their homolog and isomer distributions, and the presence of free 1,7-triacontanediol, possible biosynthetic reactions leading to these compounds are discussed.
- Busta, Lucas,Budke, Jessica M.,Jetter, Reinhard
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- SYNTHESIS OF OLEFINIC ALCOHOLS VIA ENZYMATIC TERMINAL HYDROXYLATION
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In certain aspects, the present invention provides methods for producing terminally hydroxylated alkenes and alkynes by contacting an unsaturated or saturated hydrocarbon substrate with a hydroxylase enzyme. Exemplary terminal hydroxylases useful for carrying out the methods of the invention exhibit strong selectivity towards one terminal carbon of a hydrocarbon substrate and include, but are not limited to, non-heme diiron alkane monooxygenases, cytochromes P450 (e.g., cytochromes P450 of the CYP52 and CYP153 family), as well as long chain alkane hydroxylases. In some embodiments, the terminally hydroxylated alkene or alkyne is further converted to a terminal alkenal. In certain embodiments, terminally hydroxylated alkenes and alkynes are useful as insect pheromones which modify insect behavior. In other embodiments, terminally hydroxylated alkenes and alkynes are useful intermediates for producing pheromones via acetylation or oxidation of the alcohol moiety.
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Paragraph 0315; 0317
(2016/01/30)
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- Carbon nanotube adsorptive materials derived from acid degradable poly(acetals)
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In this paper, we report the synthesis and characterization of a well-controlled and acid degradable poly(acetal) which can adsorb strongly to the surface of carbon nanotubes (CNTs). These polymers, generated via acyclic diene metathesis (ADMET), incorporate pendant pyrene groups that are well-known to associate strongly to CNTs by noncovalent interactions. Films and solutions of the polymer were degraded through the controlled addition of aqueous hydrochloric acid in ethanol. The polymer's ability to adsorb to and be removed from a CNT film was also evaluated.
- Spring, Andrew M.,Estrada, Leandro A.,Vasilyeva, Svetlana V.,Rinzler, Andrew G.,Reynolds, John R.
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p. 2556 - 2560
(2014/05/06)
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- Sphingosine Analogs, Compositions, and Methods Related Thereto
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The disclosure relates to compounds, pharmaceutical compositions, and methods of treating or preventing disease. In certain embodiments, the disclosure relates to methods of treating an infection or cancer comprising administering a pharmaceutical composition disclosed herein to a subject in need thereof. In a typical embodiment, one administers a pharmaceutical composition comprising sphingosine or a sphingosine analog to a subject at risk for, exhibiting symptoms of or diagnosed with a malaria infection.
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Paragraph 0214; 0215
(2014/10/29)
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- Design, Synthesis, and Antibacterial Activity of Demethylvancomycin Analogues against Drug-Resistant Bacteria
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Five novel N-substituted demethylvancomycin derivatives were rationally designed and synthesized by using a structure-based approach. The invitro antibacterial activities against methicillin-resistant Staphylococcus aureus (MRSA), gentamicin-resistant Enterococcus faecalis (GRE), methicillin-resistant Streptococcus pneumoniae (MRS), and vancomycin-resistant Enterococcus faecalis (VRE) were evaluated. One of the compounds, N-(6-phenylheptyl)demethylvancomycin (12a), was found to exhibit more potent antibacterial activity than vancomycin and demethylvancomycin. Compound 12a was also found to be ~18-fold more efficacious than vancomycin against MRSA; however, the two compounds were found to have similar efficacy against MRS. Furthermore, compound 12a exhibited a favorable pharmacokinetic profile with a half-life of 5.11±0.52h, which is longer than that of vancomycin (4.3±1.9h). These results suggest that 12a is a promising antibacterial drug candidate for further preclinical evaluation.
- Chang, Jun,Zhang, Si-Ji,Jiang, Yong-Wei,Xu, Liang,Yu, Jian-Ming,Zhou, Wen-Jiang,Sun, Xun
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p. 976 - 984
(2013/07/27)
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- Long-chain triazolyl acids as inhibitors of osteoclastogenesis
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Saturated fatty acids (e.g., palmitic acid) are known to moderately inhibit the development of osteoclasts in vitro. In pursuit of more effective inhibitors of osteoclastogenesis we explored two new classes of palmitic acid analogues containing either an ether or triazolyl group at various positions along the chain. The compounds were evaluated for their ability to inhibit the formation of osteoclasts in primary mouse bone marrow cultures. The oxyacids were generally prepared by condensation of the appropriate alkyl halides and diols, followed by Jones oxidation. The triazolyl acids were prepared by copper-catalysed click chemistry between alkyl azides and acetylenic acids, or with the appropriately-protected azides and alkynes, followed by deprotection and oxidation. The oxyacids were little more effective than palmitic acid, but the triazolyl analogues were much more effective osteoclastogenesis inhibitors, especially when the triazole was distant from the acid unit.
- Marshall, Andrew J.,Lin, Jian-Ming,Grey, Andrew,Reid, Ian R.,Cornish, Jillian,Denny, William A.
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p. 4112 - 4119
(2013/07/27)
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- Synthesis and polymerization kinetics of acrylamide phosphonic acids and esters as new dentine adhesives
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In restorative dentistry, acrylamide monomers bearing phosphonic acid moieties have proved to be useful species for the formulation of dental self-etch adhesives since they provide enhanced adhesion to hydroxyapatite and are not subject to hydrolysis, thus potentially improving their adhesive durability. Previous studies have demonstrated that phosphonic acid acrylamides increase the rate of photopolymerization of diacrylamide monomers. To understand whether this rate acceleration is specific to the acrylamide function of the monomer, or due to the phosphonic acid group per se, or is applicable only with a crosslinking reaction, we have synthesized several acrylamide and methacrylate monomers bearing phosphonic acid or phosphonate moieties and studied their photopolymerization kinetics. The acrylamide phosphonic acid was found to accelerate the polymerization rate but similar monomers bearing a phosphonate ester group had a much smaller effect. A similar accelerating effect was observed when the phosphonic acid-based monomers were copolymerized with a monofunctional acrylamide monomer, excluding the possibility that the rate acceleration might be related to the crosslinking process. This rate effect is also observed when a nonpolymerizable organic phosphonic acid is present in the polymerizing medium. We suggest that the increase of the medium polarity is responsible for this rate enhancement effect.
- Besse,Le Pluart,Cook,Pham,Madec
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p. 149 - 157
(2013/01/16)
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- Alkylboronic esters from palladium- and nickel-catalyzed borylation of primary and secondary alkyl bromides
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Palladium- and nickel-catalyzed cross-coupling recations of unactivated alkyl bromides with diboron reagents have been developed as practical methods for the synthesis of primary and secondary alkylboronic esters. These reactions extend the concept and utility of Pd- and Ni-catalyzed cross-coupling of aliphatic electrophiles. They also show different substrate selectivity and ligand dependence as compared to the recently reported Cu-catalyzed borylation reaction. Copyright
- Yi, Jun,Liu, Jin-Hui,Liang, Jun,Dai, Jian-Jun,Yang, Chu-Ting,Fu, Yao,Liu, Lei
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supporting information; experimental part
p. 1685 - 1691
(2012/07/28)
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- Sphingolipid analogues inhibit development of malaria parasites
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Plasmodium-infected erythrocytes have been shown to employ sphingolipids from both endogenous metabolism as well as existing host pools. Therapeutic agents that limit these supplies have thus emerged as intriguing, mechanistically distinct putative targets for the treatment of malaria infections. In an initial screen of our library of sphingolipid pathway modulators for efficacy against two strains of the predominant human malaria species Plasmodium falciparum and Plasmodium knowlesi, a series of orally available, 1-deoxysphingoid bases were found to possess promising in vitro antimalarial activity. To better understand the structural requirements that are necessary for this observed activity, a second series of modified analogues were prepared and evaluated. Initial pharmacokinetic assessments of key analogues were investigated to evaluate plasma and red blood cell concentrations in vivo.
- Meyer, Esmeralda V. S.,Holt, Jason J.,Girard, Kathryn R.,Ballie, Mark T.,Bushnev, Anatoliy S.,Lapp, Stacey,Menaldino, David S.,Arrendale, Richard F.,Reddy, G. Prabhakar,Evers, Taylor J.,Howard, Randy B.,Culver, Deborah G.,Liotta, Dennis C.,Galinski, Mary R.,Natchus, Michael G.
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supporting information; experimental part
p. 43 - 47
(2012/04/04)
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- DI-SUBSTITUTED PYRIDINUM POLYMERS AND SYNTHESIS THEREOF
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A method of producing a di-substituted pyridinium polymer by microwave-assisted polymerisation of a 2, 3, or 4-substituted pyridine monomer of the formula NC5R4—R′—X, wherein R is selected from hydrogen, hydroxyl, and substituted or unsubstituted alkyl, alkoxy, aryl, alkaryl, aralkyl, and alkenyl groups, R′ is a linking group, and X is a leaving group. Using this method, di-substituted pyridinium polymer compositions may be obtained wherein at least 50% of the di- substituted pyridinium polymer chains in the composition have the same degree of polymerisation.
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Page/Page column 4-5
(2012/05/21)
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- Halogenation of primary alcohols using a tetraethylammonium halide/[Et 2NSF2]BF4 combination
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The halogenation of primary alcohols is presented. The use of a combination of tetraethylammonium halide and [Et2NSF2]BF4 (XtalFluor-E) allows for chlorination and bromination reactions to proceed efficiently (up to 92% yield) with a wide range of alcohols. Iodination reactions are also possible albeit in lower yields.
- Pouliot, Marie-France,Mahe, Olivier,Hamel, Jean-Denys,Desroches, Justine,Paquin, Jean-Francois
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supporting information
p. 5428 - 5431,4
(2020/10/15)
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- Efficient synthesis of unsaturated 1-monoacyl glycerols for in meso crystallization of membrane proteins
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A highly efficient synthesis of unsaturated 1-monoacyl glycerols was established to fulfill the pressing need for materials that form lipidic mesophases utilized in membrane protein crystallization. Georg Thieme Verlag Stuttgart.
- Fu, Yu,Weng, Yue,Hong, Wen-Xu,Zhang, Qinghai
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experimental part
p. 809 - 812
(2011/06/21)
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- Synthesis of highly enantioenriched hydroxy- and dihydroxy-fatty esters: Substrate precursors for cytochrome P450BioI
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A series of highly enantioenriched hydroxy- and dihydroxy-fatty esters were required as part of our ongoing investigation into cytochrome P450 BioI. This mediates the biosynthesis of pimelic acid via C-C bond cleavage of long chain fatty acids within Bacillus subtilis. Herein we report the synthesis of various stereoisomers of methyl 7-hydroxytetradecanoate, methyl 8-hydroxytetradecanoate, and methyl 7,8-dihydroxytetradecanoate in highly enantioenriched form, using a combination of asymmetric synthesis and a preparative enantioselective HPLC is reported.
- Singh, Arti A.,Zulkifli, Siti N.A.,Meyns, Michaela,Hayes, Patricia Y.,De Voss, James J.
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scheme or table
p. 1709 - 1719
(2012/02/06)
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- COMPOUND, POLYMERIZABLE LIQUID CRYSTALLINE COMPOSITION, OPTICAL ELEMENT, AND OPTICAL INFORMATION RECORDING/REPRODUCTION DEVICE
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A compound having a good durability against light and capable of producing desired liquid crystallinity after polymerization, and a polymerizable liquid crystal composition containing such a compound, are provided. Further, an optical element having a good durability against light, and an optical information writing/reading device employing such an element, are provided. A compound represented by CH2 =CR1 -COO-R2 -Cy-Ph-R3 -OCO-CR4 =CH2. R1 and R4 are each preferably a hydrogen atom. R3 is preferably a C1-6 alkylene group wherein an oxygen atom is present or not present at an end of the group to be bonded to a cyclic group, and wherein some or all of hydrogen atoms bonded to carbon atoms in the group may be substituted by fluorine atoms; or an alkylene group wherein an oxygen atom is present at an end of the group to be bonded to a cyclic group. A diffraction grating 2 produced by employing this liquid crystal compound has a good durability against light, and accordingly, it is possible to constitute an optical information writing/reading device suitable for large capacity recording by employing a blue laser as a light source 1.
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Page/Page column 10-12
(2011/04/18)
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- INTERLOCKED MOLECULES AND RELATED COMPONENTS, COMPOSITIONS, MATERIALS, METHODS AND SYSTEMS
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[c2] daisy chain macromers, dimers and polymers and related compositions, materials, methods and systems are described.
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Page/Page column 12-13
(2011/04/18)
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- Investigation of spacer influences in phosphorescent-emitting nonconjugated PLED systems
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An assay was introduced to clarify influences on electroluminescent behavior for RGB-colored phosphorescent terpolymers with N,N-Di-p-tolyl-aniline as hole-transporting unit, 2-(4-biphenyl)-5-(4-tert-butylphenyl)-1,3,4- oxadiazole (tert- BuPBD) as electron-transporting unit, and different iridium complexes in RGB-colors as triplet emitting materials. All monomers were attached with spacer moieties to the "para" position of a polystyrene. Polymer light emitting diodes (PLEDs) were built to study the electro-optical behavior of these materials. The gist was a remarkable influence of hexyl-spacer units to the PLED performance. For all three colors only very restricted PLED performances were found. In comparison RGB-terpolymers were synthesized with directly attached charge transport materials to the polymer backbone. For this directly linked systems efficiencies were 28 cd A-1 @ 6 V (green), 4.9 cd A-1 @ 5 V (red) and 4.3 cd A-1 @ 6 V (bluish). In summary we assume that an improved charge percolation pathways regarding to the higher content of semiconducting molecules and an improved charge transfer to the phosphorescent dopand in the case of the copolymers without spacers are responsible for the better device performance comparing the copolymers with hexyl spacers. The approach of the directly connected charge transport materials at the nonconjugated styrene polymer backbone should be favored for further investigations, therefore.
- Thesen, Manuel W.,Krueger, Hartmut,Janietz, Silvia,Wedel, Armin,Graf, Marion
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experimental part
p. 389 - 402
(2010/11/04)
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- Switching and extension of a [c2]daisy-chain dimer polymer
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(Chemical Equation Presented) We report the synthesis of a [c2]daisy-chain dimer via ruthenium-catalyzed ring-closing olefin metathesis. Confirmation of the interlocked nature of the structure was achieved through single-crystal X-ray diffraction analysis. The dimer could be readily switched from the bound to the unbound conformation by treatment with 3.0 equiv of KOH and subsequently reprotonated by treatment with 3.0 equiv of HPF6. Azide functionalization of the dimer enabled incorporation in linear step-growth polymer chains using the alkyne-azide "click" reaction. Gel permeation chromatography coupled with multiangle laser light scattering analysis showed the polymers contained 22 dimers and had a radius of gyration of 14.8 nm. Acylation of the amines of the dimers sterically forced elongation of the interlocked units, and MALLS analysis of the polymer showed a 48% increase in the Rg (21.4 nm).
- Clark, Paul G.,Day, Michael W.,Grubbs, Robert H.
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supporting information; experimental part
p. 13631 - 13633
(2010/01/06)
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- THERAPEUTICALLY ACTIVE TRIAZOLES AND THEIR USE
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This invention relates to novel estratrien-triazoles of general formula (I) useful in therapy, especially for use in the treatment and/or prevention of a steroid hormone dependent disorder, preferably a steroid hormone dependent disease or disorder requiring the inhibition of a 17beta-hydroxysteroid dehydrogenase (17beta-HSD) such as 17beta-HSD type 1, type 2 or type 3 enzyme.
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Page/Page column 68
(2008/06/13)
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- Therapeutically Active Triazoles and Their Use
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Estratrien-triazoles corresponding to formula (I) (shown below) which are useful in therapy, especially for the treatment and/or prevention or inhibition of a steroid hormone dependent disorder, preferably a steroid hormone dependent disease or disorder requiring the inhibition of a 17β-hydroxysteroid dehydrogenase (17β-HSD) such as 17β-HSD type 1, type 2 or type 3 enzyme.
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Page/Page column 31
(2008/12/06)
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- Microwave and ultrasound assisted synthesis of 16-methyl-8(Z)-heptadecenoic and 16-methyl-6(Z)-heptadecenoic acids
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The first total synthesis of two novel iso-branched heptadecenoic acids, the major components in a species of bacterium, Micrococcus, has been carried out using a rapid, simple and clean process utilizing microwave and ultrasound radiations.
- Kaur, Jasamrit,Kaur, Irvinder,Sonu,Kad, Goverdhan L.,Singh, Jasvinder
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p. 155 - 158
(2008/09/20)
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- Primary alkyl bromides from dimethylthiocarbamates
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The conversion of primary alkyl dimethylthiocarbamates into alkyl bromides using the Vilsmeier reagent occurs in high yields in the presence of other non-acid sensitive and non-nucleophilic functional groups. Georg Thieme Verlag Stuttgart · New York.
- Moynihan, Meghan F.,Tucker, Joseph W.,Abelt, Christopher J.
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experimental part
p. 3565 - 3568
(2009/06/18)
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- Efficient role of ionic liquid (bmim)HSO4 as novel catalyst for monotetrahydropyranylation of diols and tetrahydropyranylation of alcohols
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A simple procedure for the monotetrahydropyranylation of diols and alcohols, in excellent to moderate yields, has been reported using a catalytic amount of the acidic ionic liquid, 1-butyl-3-methylimidazolium hydrogensulphate (bmim)HSO4 under microwave and ultrasonic irradiation. Results have been compared with those obtained by reactions in the absence of these energies, and effectiveness of the recycled ionic liquid has also been studied. Copyright Taylor & Francis Group, LLC.
- Singh, Jasvinder,Gupta, Neeraj,Kad, Goverdhan L.,Kaur, Jasamrit
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p. 2893 - 2900
(2007/10/03)
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- Synthesis and structure-activity relationship effects on the tumor avidity of radioiodinated phospholipid ether analogues
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Radioiodinated phospholipid ether analogues have shown a remarkable ability to selectively accumulate in a variety of human and animal tumors in xenograft and spontaneous tumor rodent models. It is believed that this tumor avidity arises as a consequence of metabolic differences between tumor and corresponding normal tissues. The results of this study indicate that one factor in the tumor retention of these compounds in tumors is the length of the alkyl chain that determines their hydrophobic properties. Decreasing the chain length from C12 to C7 resulted in little or no tumor accumulation and rapid clearance of the compound in tumor-bearing rats within 24 h of administration. Increasing the chain length had the opposite effect, with the C15 and C18 analogues displaying delayed plasma clearance and enhanced tumor uptake and retention in tumor-bearing rats. Tumor uptake displayed by propanediol analogues NM-412 and NM-413 was accompanied by high levels of liver and abdominal radioactivity 24 h postinjection to tumor-bearing rats. Addition of a 2-O-methyl moiety to the propanediol backbone also retarded tumor uptake significantly. A direct comparison between NM-404 and its predecessor, NM-324, in human PC-3 tumor bearing immune-compromised mice revealed a dramatic enhancement in both tumor uptake and total body elimination of NM-404 relative to NM-324. On the basis of imaging and tissue distribution studies in several rodent tumor models, the C18 analogue, NM-404, was chosen for follow-up evaluation in human lung cancer patients. Preliminary results have been extremely promising in that selective uptake and retention of the agent in tumors is accompanied by rapid clearance of background radioactivity from normal tissues, especially those in the abdomen. These results strongly suggest that extension of the human trials to include other cancers is warranted, especially when NM-404 is radiolabeled with iodine-124, a new commercially available positron-emitting isotope. The relatively long physical half-life of 4 days afforded by this isotope appears well-suited to the pharmacodynamic profile of NM-404.
- Pinchuk, Anatoly N.,Rampy, Mark A.,Longino, Marc A.,Skinner, R. W. Scott,Gross, Milton D.,Weichert, Jamey P.,Counsell, Raymond E.
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p. 2155 - 2165
(2007/10/03)
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- Preparation of para-terphenylylalkanethiols with different chain lengths
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Terphenylylalkanethiols with different chain length were synthesized using palladium-catalyzed cross-coupling reactions. While the thiols with two and three methylene groups were obtained via photoaddition of thiopivalic acid to the respective alkenes, the longer terphenylylalkanethiols were synthesized by two consecutive Kumada cross-coupling reactions followed by a Mitsunobu reaction for the introduction of the sulfur functionality. Georg Thieme Verlag Stuttgart.
- Mueller, Jan,Brunnbauer, Markus,Schmidt, Michael,Zimmermann, Anja,Terfort, Andreas
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p. 998 - 1004
(2007/10/03)
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- Concise synthesis of (8Z,11Z,14Z)-8,11,14-heptadecatrienal, (7Z,10Z,13Z)-7,10,13-hexadecatrienal, and (8Z,11Z)-8,11-heptadecadienal, components of the essential oil of marine green alga Ulva pertusa
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The long-chain aldehydes, (8Z,11Z,14Z)-8,11,14-heptadecatrienal, (7Z,10Z,13Z)-7,10,13-hexadecatrienal, and (8Z,11Z)-8,11-heptadecadienal, were concisely synthesized by using Grignard coupling, catalytic hydrogenation with the Lindlar catalyst, and oxidation with Dess-Martin periodinane as the key steps. Particularly, (8Z,11Z,14Z)-8,11,14-heptadecatrienal and (7Z,10Z, 13Z)-7,10,13-hexadecatrienal both possessed a seaweed-like odor.
- Akakabe, Yoshihiko,Washizu, Kensuke,Matsui, Kenji,Kajiwara, Tadahiko
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p. 1348 - 1352
(2008/02/01)
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- Estrogen-linked platinum (II) complexes as anticancer agents
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wherein n may be 1, 2, 3, 4 or 5 when X is O, wherein n may be 2/3, 1, 4/3, 5/3, 2, 7/3, 8/3, 3, or 10/3 when X is C, wherein o may be 1, 2 or 3, wherein Y may be O or 17β-OH, wherein R1 may be selected from the group consisting of H, a straight alkyl group of 1 to 5 carbon atoms, a branched alkyl group of 3 to 5 carbon atoms, wherein R2 may be selected for the group consisting of H, a straight alkyl group of 1 to 4 carbon atoms, a branched alkyl group of 3 or 4 carbon atoms, F, Cl, Br, I, —CF3, —NO2, —OR1, —COR1 and —CH2OH. These compounds possess anticancer activity against hormono-dependent breast, uterus as well as ovarian cancer.
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Page/Page column 5
(2008/06/13)
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- Total synthesis and assignment of the double-bond position and absolute configuration of (-)-pyrinodemin A
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(Matrix presented) The first asymmetric total synthesis of a structurally novel cis-cyclopent[c]isoxazolidine alkaloid, (-)-pyrinodemin A (3), which exhibits potent cytotoxicity, has been accomplished through a highly diastereoselective intramolecular nitrone - olefin cycloaddition reaction as the key step. Thus, it has been found that the hitherto unknown absolute configuration of pyrinodemin A is as indicated in the structural formula 3.
- Morimoto, Yoshiki,Kitao, Satoru,Okita, Tatsuya,Shoji, Takamasa
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p. 2611 - 2614
(2007/10/03)
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- CONDUCTIVE ORGANIC THIN FILM, PROCESS FOR PRODUCING THE SAME, ELECTRONIC DEVICE EMPLOYING THE SAME, ELECTRICAL CABLE, ELECTRODE, PYRROLYL COMPOUND, AND THEIENYL COMPOUND
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It is an object to provide a conductive organic thin film having organic molecules that include at one end a terminal bonding group that is covalently bonded to a substrate surface, a conjugate bonding group that is located at any portion of the organic molecules and that is polymerized with other molecules, and a polar functional group that does not include active hydrogen and that is located at any portion between the terminal bonding group and the conjugate bonding group, wherein the organic molecules are oriented and their conjugate bonding groups are polymerized, forming a conduction network. The conductivity (ρ) of the conductive organic thin film at room temperature (25°C) is at least 5.5 × 105 S/cm, and preferably at least 1×( 107 S/cm, without dopants, having significantly higher conductivity than metals such as gold and silver. In particular, a film of polypyrrole or polythienylene conjugate bonds that is polymerized through polymerization through electrolytic oxidation has high conductivity.
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- Convenient and convergent syntheses of long-chain α,ω-dibromides and diphosphines of the formula X(CH2)nX (n = 18-32)
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The known tetrahydropyranyl ethers Br(CH2)yOTHP (y = 6, 9, 11), which are easily prepared from commercial bromoalcohols, are sequentially treated with Mg, Li2CuCl4, and X(CH2)2X (z/X = 6/Br, 7/Br, 8/Br, 10/Br, 10/I) to give the diethers THPO(CH2)nOTHP in 68-40% yields (n = 2 y + z = 18, 19, 20, 22, 24, 28, 32). Subsequent reactions with Ph3P and 2,4,4,6-tetrabromocyclohexa-2,5-dienone give the title compounds Br(CH2)nBr in 91-75% yields. Reactions with commercial K+PPh2 give the diphosphines Ph2P(CH2)nPPh2 in 95-74% yields.
- Mohr, Wolfgang,Horn, Clemens R.,Stahl, Juergen,Gladysz
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p. 1279 - 1285
(2007/10/03)
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- POLYMERIZABLE COMPOSITION SHOWING LIQUID-CRYSTAL PHASE AND OPTICALLY ANISOTROPIC OBJECT MADE WITH THE SAME
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An object of the present invention is to provide a polymerizable liquid crystal composition incorporating a polymerizable liquid crystal compound which displays a low nematic phase temperature, displays excellent compatibility with other polymerizable liquid crystal compounds, and furthermore yields a product following polymerization, of good transparency and high mechanical strength. A polymerizable composition is provided which displays a liquid crystal phase, and moreover incorporates a liquid crystal backbone with two or more ring structures and a compound with a partial structure represented by the general formulaP-S-A-D-E- [wherein P1 represents a polymerizable functional group; S1 represents -(CH2)w-, - O(CH2)w-, -(CH2)wO-, -(CH2)wC(=O)O-, -(CH2)wOC(=O)-, -C(=O)O(CH2)w- or - OC(=O)(CH2)w- (w: 1 to 20); A1 and E1 each represent a hydrocarbon ring or a hetero ring, although E1 is a ring incorporated within the liquid crystal backbone; and D1 represents - C(=O)-O-(CH2)m-O-, -O(CH2)m-O-C(=O)-, -O-C(=O)-(CH2)m-O-, or -O(CH2)m-C(=O)-O- (m: 1 to 15)].
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- Structure-activity relationships in platelet-activating factor (PAF). 11-From PAF-antagonism to phospholipase A2 inhibition: Syntheses and structure-activity relationships in 1-arylsulfamido-2-alkylpiperazines
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1-Benzoyl-2-alkyl piperazines are strong inhibitors of Group I and II secreted PLA2s. An improvement of their activity was obtained by replacing the amide function by a sulfamide and by introduction of electrodonor substituents on the para position of the benzenesulfonyl moiety. Neither the position on one of the carbon of the piperazine ring nor the absolute configuration of this carbon have an effect on the affinity for one or the other group of PLA2, but the lipophilicity remains for these series an essential parameter. In addition structure-activity relationships allow new hypothesis on interaction of these piperazine derivatives with the catalytic site of PLA2s.
- Binisti, Carine,Assogba, Leon,Touboul, Estera,Mounier, Carine,Huet, Jack,Ombetta, Jean-Edouard,Dong, Chang Zhi,Redeuilh, Catherine,Heymans, Francoise,Godfroid, Jean-Jacques
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p. 809 - 828
(2007/10/03)
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- Ultrasound mediated synthesis of a few naturally occurring compounds
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Synthesis of 2-methylheptadecane 1, 14-methylpentadecan-3-one 2, 6-oxo-1-nonanol 3, 5-(Z)-undecenoic acid 4 and 2-tridecanone 5 have been accomplished utilizing zinc-copper couple catalyzed conjugate addition of α,β-unsaturated carbonyl compounds under aqueous sonochemical conditions as the key step.
- Singh,Kaur,Nayyar,Bhandari,Kad
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p. 386 - 390
(2007/10/03)
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- Synthesis of E-9-dodecen-1-yl acetate using organomanganese reagents
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The Grignard reagent obtained from 2-(6-bromohexyloxy)-tetrahydropyrane, by treatment with anhydrous manganese(II) chloride was transformed to the corresponding organomanganese reagent, which was coupled with E-1-bromo-3-hexene by treatment with anhydrous manganese chloride. Further deprotection and acetylation furnished E-9-dodecen-1-yl acetate. A second procedure involved the coupling of E-3-hexenylmanganese bromide and 6-bromohexyl acetate. Coupling reactions were carried out at 0 °C, using tetrahydrofurane and N-methylpyrrolidone as co-solvent.
- Belmar, Julio,Tellez,Baeza,Freer
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p. 583 - 586
(2007/10/03)
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- Sex pheromone of female vine bud moth, Theresimima ampellophaga comprises (2s)-butyl (7z)-tetradecenoate
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The sex pheromone of the vine bud moth, Theresimima ampellophaga, released at the 3rd-5th abdominal tergites, was identified by coupled GC-EAG, GC-MS, and synthesis as (2S)-butyl (7Z)-tetradecenoate. For the first time, full stereochemistry is unambiguously defined for the sex pheromone of a member of the Zygaenidae. The synthetic compound caught significant numbers of males in field-trapping experiments.
- Subchev,Harizanov,Francke,Franke,Plass,Reckziegel,Schroeder,Pickett,Wadhams,Woodcock
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p. 1141 - 1151
(2007/10/03)
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- Functionalized aliphatic P2/P2' analogs of HIV-1 protease inhibitor DMP323
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A series of analogs of HIV protease inhibitor DMP323 containing functionalized aliphatic P2/P2' groups was prepared and evaluated for HIV protease inhibition and antiviral activity in a cell-based assay. Asymmetric compounds with a 5-hydroxypentyl substituent at P2 and a benzylic substituent at P2' showed increased potency over the corresponding symmetrically substituted analogs.
- Smallheer, Joanne M.,McHugh, Robert J.,Chang, Chong-Hwan,Kaltenbach III, Robert F.,Worley, Tabitha V.,Klabe, Ronald M.,Bacheler, Lee T.,Rayner, Marlene M.,Erickson-Viitanen, Susan,Seitz, Steven P.
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p. 1365 - 1370
(2007/10/03)
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- Synthesis of (R,S)-10-methyloctadecanoic acid (tuberculostearic acid) and key chiral 2-methyl branched intermediates
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Tuberculostearic acid (R)-10-methyloctadecanoic acid, is a characteristic component of pathogenic mycobacteria and related organisms.Sensitive detection of this acid infected material allows rapid detection of mycobacterial disease.A novel, convergent synthesis of tuberculostearic acid and key chiral intermediates is described in this communication, to provide a reference compound.Racemic and (R)- and (S)-1-iodo-2-methyldecanes were synthesised from 1-octanal and 1-carboethoxyethylidenetriphenylphosphorane as initial starting materials. 1-Hydroxyoct-7-yne was made from 1,6-hexanediol by two alternative methods and coupled with the above racemic iodide.Hydrogenation and oxidation of the resulting (R,S)-10-methyloctadec-7-yn-1-ol gave racemic tuberculostearic acid. Keywords: Mycobacterium tuberculosis; Tuberculostearic acid; Acetylene coupling; (R,S)-10-methyloctadecanoic acid; Chiral 2-methyl branched fatty acids
- Wallace, Paul A.,Minnikin, David E.,McCrudden, Katharine,Pizzarello, Andrea
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p. 145 - 162
(2007/10/02)
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- Synthesis of Functionalised 12-,13- and 14-Membered Crown Ethers Bearing Exocyclic Polymerisable Groups and the Binding Properties and Conductivities of their Lithium Doped Polymers
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The synthesis of a series of , and -membered crown ethers bearing an exocyclic polymerisable methacrylate is reported.The spacing group between the ring and the methacrylate is either a simple alkyl chain, or 6, or an oxydiethylene chain.The relative binding ability of the "mono and di-substituted" macrocyclic rings towards Li+ is compared by 13C NMR analysis.Radical polymerisation gives the amorphous polymers in which the glass transition temperature is primarily controlled by the nature of the spacer group.In the lithium doped polymers, for a given glass transition temperature, Tg, the -ring materials show enhanced ionic conductivities over the -ring analogues which may be related to the lower rate of lithium exchange (in the former series) or to an enhanced tendency of the -ring systems to form 2:1 complexes with more effective counterion separation.
- Collie, Luke,Denness, James E.,Parker, David,O'Carroll, Fiona,Tachon, Christine
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p. 1747 - 1758
(2007/10/02)
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- Pheromone Evaluation of Four Geometric Isomers of 4,11-Hexadecadienal toward Male Eri-Silk Moths
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Four geometric isomers of 4,11-hexadecadienal were prepared and their pheromone activities to male eri-silk moths were evaluated by using the fluttering test and electro-antennography.None of these compounds showed any activity in spite of their similar structure to other pheromone mimics and to the natural pheromone.These results suggest that the presence of 6,11-double bonds is essential for pheromone activity.
- Tomida, Ichiro,Mayesawa, Tsuneaki
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p. 1962 - 1965
(2007/10/02)
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- 88. Synthesis of the Brentonins, Polyolefinic Esterified Glyceryl Ethers of an Unidentified Sponge from the North-Brittany Sea: Absolute Configuration and Novel Structure Assignment
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The absulute configurations of acetylated bretonin A (= (+)-(R)-1--2-oxy>ethyl 4-acetoxybenzoate; (-)-1b) and isobretonin A (= (+)-(S)-3-oxy>-2-hydroxypropyl 4-hydroxybenzoate; (+)-2), previously isolated from an undetermined sponge of the North Brittany sea, were established by comparison with synthetic (+)-1b and (+)-2, obtained from the condensation of commercial (-)-(R)-2,2-dimethyl-1,3-dioxolan-4-yl p-toluenesulfonate ((-)-(R)-15) with a mixture of (4E,6E,8E)- (14e) and (4E,6Z,8E)-dodeca-4,6,8-trien-1-ol (14z).This also allowed confirming the structure and configuration of bretonin B (= (S)-2-oxy>-1-(hydroxymethyl)ethyl 4 hydroxybenzoate; 3) which was also isolated from the same sponge, albeit in a too small amount for a complete study.As concerns the glyceryl ethers precursers of the bretonins, co-occurene of the usual (S)-configuration (from 1a) with the unusual (R)-configuration (from (+)-2) poses intriguing biogenetic problems.
- Mancini, Ines,Guella, Graziano,Pietra, Francesco
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p. 941 - 950
(2007/10/02)
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- INTRAMOLECULAR DIELS-ALDER REACTIONS OF SULPHONYL-SUBSTITUTED TRIENES
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The synthesis and thermal intramolecular Diels-Alder reactions of a series of sulphonyl-substituted deca-, undeca- and dodecatrienes have been carried out.The stereoselectivities of these reactions are discussed, and methylation reactions of the bicyclic products are described.
- Craig, Donald,Fischer, Doris A.,Kemal, Oeznur,Marsh, Andrew,Plessner, Thomas,et al.
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p. 3095 - 3128
(2007/10/02)
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- Synthesis of Large Macrocyclic Tetraaza Compounds with A Methylene Backbone: Cyclo4, (n = 6,7,8,9 and 10). The Formation of 28-, 32-, 36-, 40- and 44-Membered Rings.
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A series of macrocyclic tetraamines with 28-, 32-, 36-, 40- and 44-membered rings have been efficiently prepared from the corresponding ditosylamide and monobromoalcohol derivatives in 6 steps via a double condensation reaction.Overall yields were: 41, 41, 46, 29, and 33 percent, respectively, for 1,8,15,22-tetraazacyclooctacontane (11a), 1,9,17,25-tetraazacyclodotriacontane (11b), 1,10,19,28, tetraazacyclohexatriacontane (11c), 1,11,21,31-tetraazacyclotetracontane (11d) and 1,12,23,34-tetraazacyclotetratetracontane (11e).
- Tomohiro, Takenori,Uoto, Kouichi,Okuno, Hiroaki (Yohmei)
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p. 1233 - 1239
(2007/10/02)
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