- Targeting Tumor Associated Phosphatidylserine with New Zinc Dipicolylamine-Based Drug Conjugates
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A series of zinc(II) dipicolylamine (ZnDPA)-based drug conjugates have been synthesized to probe the potential of phosphatidylserine (PS) as a new antigen for small molecule drug conjugate (SMDC) development. Using in vitro cytotoxicity and plasma stability studies, PS-binding assay, in vivo pharmacokinetic studies, and maximum tolerated dose profiles, we provided a roadmap and the key parameters required for the development of the ZnDPA based drug conjugate. In particular, conjugate 24 induced tumor regression in the COLO 205 xenograft model and exhibited a more potent antitumor effect with a 70% reduction of cytotoxic payload compared to that of the marketed irinotecan when dosed at the same regimen. In addition to the validation of PS as an effective pharmacodelivery target for SMDC, our work also provided the foundation that, if applicable, a variety of therapeutic agents could be conjugated in the same manner to treat other PS-associated diseases.
- Liu, Yu-Wei,Shia, Kak-Shan,Wu, Chien-Huang,Liu, Kuan-Liang,Yeh, Yu-Cheng,Lo, Chen-Fu,Chen, Chiung-Tong,Chen, Yun-Yu,Yeh, Teng-Kuang,Chen, Wei-Han,Jan, Jiing-Jyh,Huang, Yu-Chen,Huang, Chen-Lung,Fang, Ming-Yu,Gray, Brian D.,Pak, Koon Y.,Hsu, Tsu-An,Huang, Kuan-Hsun,Tsou, Lun K.
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Read Online
- 2-Methoxy-4,6-bis(trifluoromethyl)phenyllithium: A new stable aryllithium useful as an intermediate to bis(trifluoromethyl)aromatics
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A method for the preparation of 3,5-bis(trifluoromethyl)anisole (3) has been developed. Lithiation of 3 occurred exclusively at the position ortho to the CH3O group to give a thermally stable lithium derivative 6 which readily undergoes conventional reactions with a number of electrophiles. Formylation and carboxylation of 6 gave bis(trifluoromethyl) derivatives of salicylic aldehyde and salicylic acid 9-12 in good yields.
- Dmowski, Wojciech,Piasecka-Maciejewska, Krystyna
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Read Online
- Mechanical Properties of a Metal-Organic Framework formed by Covalent Cross-Linking of Metal-Organic Polyhedra
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Overcoming the brittleness of metal-organic frameworks (MOFs) is a challenge for industrial applications. To increase the mechanical strength, MOFs have been blended with polymers to form composites. However, this also brings challenges, such as integration and integrity of MOF in the composite, which can hamper the selectivity of gas separations. In this report, an "all MOF" material with mechanical flexibility has been prepared by covalent cross-linking of metal-organic polyhedra (MOPs). The ubiquitous Cu24 isophthalate MOP has been decorated with a long alkyl chain having terminal alkene functionalities so that MOPs can be cross-linked via olefin metathesis using Grubbs second generation catalyst. Different degrees of cross-linked MOP materials have been obtained by varying the amount of catalyst in the reaction. Rheology of these structures with varying number of cross-links was performed to assess the cross-link density and its homogeneity throughout the sample. The mechanical properties were further investigated by the nanoindentation method, which showed increasing hardness with higher cross-link density. Thus, this strategy of cross-linking MOPs with covalent flexible units allows us to create MOFs of increasing mechanical strength while retaining the MOP cavities.
- Lal, Garima,Derakhshandeh, Maziar,Akhtar, Farid,Spasyuk, Denis M.,Lin, Jian-Bin,Trifkovic, Milana,Shimizu, George K. H.
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- Synthesis of poly(aryl benzyl ether) dendrimers on solid support
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Dendronized supports, combining core Wang resin and poly(aryl benzyl ether) dendrons, were prepared using a novel route. Employing a dimethyl 5-hydroxyisophthalate module and a Mitsunobu condensation/ester reduction iterative sequence, the dendrimer was cleanly and efficiently prepared to the third generation. The synthesis was monitored using gel-phase 13C NMR and acidolytic cleavage, followed by 1H NMR. Gel-phase NMR and swelling experiments demonstrated that the behavior of the dendronized resins in various solvents is strongly influenced by the peripheral functional groups. Synthesis of a cinnamate derivative (via Mitsunobu and Heck reactions) and of a tripeptide demonstrated suitability of the dendronized support for solid-phase synthesis.
- Dahan, Adi,Portnoy, Moshe
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- All solution-processed red organic light-emitting diode based on a new thermally cross-linked heteroleptic Ir(iii) complex
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A novel cross-linkable red iridium(iii) complex and electron transport material were designed and synthesized for use in the fabrication of solution-processed phosphorescent organic light-emitting diodes (PHOLEDs). The newly cross-linkable red Ir(iii) complex was successfully thermal cross-linked with a cross-linkable host in the emitting layer (EML). After cross-linking, the EML was found not to be damaged by organic solvents. A maximum external quantum efficiency (EQE) of 4.64% (2.77 cd A-1) was achieved for deep-red PHOLEDs after rinsing, which was similar to the EQE of 4.59% (2.52 cd A-1) after rinsing the deep-red PHOLEDs with thermal cross-linking.
- Cho, Woosum,Reddy, Saripally Sudhaker,Kim, Junyoung,Cho, Young-Rae,Jin, Sung-Ho
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- Bispyrrolylbenzene anion receptor: From supramolecular switch to molecular logic gate
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We have designed anion receptor 4 based on a conformationally labile bispyrrolylbenzene framework, the conformation of which can be changed by appropriate anionic stimuli. In the absence of fluoride anion, the pyrrole moieties rotate freely at room temperature. However, when the concentration of fluoride anion exceeds 2 equivalents, the rotation of the pyrrole units slows down and the conformation of the receptor changes to anti-anti. DFT calculations have shown that this change is due to binding of a third fluoride anion through C-H interaction. Anion receptor 4 can also serve as a molecular logic gate. Anionic inputs such as fluoride and dihydrogenphosphate allow the realization of INHIBIT and NAND logic gate functions with absorption and fluorescence as readouts, respectively.
- Granda, Jaroslaw M.,Staszewska-Krajewska, Olga,Jurczak, Janusz
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- Multifunctional Fullerene Derivative for Interface Engineering in Perovskite Solar Cells
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In perovskite based planar heterojunction solar cells, the interface between the TiO2 compact layer and the perovskite film is critical for high photovoltaic performance. The deep trap states on the TiO2 surface induce several challenging issues, such as charge recombination loss and poor stability etc. To solve the problems, we synthesized a triblock fullerene derivative (PCBB-2CN-2C8) via rational molecular design for interface engineering in the perovskite solar cells. Modifying the TiO2 surface with the compound significantly improves charge extraction from the perovskite layer. Together with its uplifted surface work function, open circuit voltage and fill factor are dramatically increased from 0.99 to 1.06 V, and from 72.2percent to 79.1percent, respectively, resulting in 20.7percent improvement in power conversion efficiency for the best performing devices. Scrutinizing the electrical properties of this modified interfacial layer strongly suggests that PCBB-2CN-2C8 passivates the TiO2 surface and thus reduces charge recombination loss caused by the deep trap states of TiO2. The passivation effect is further proven by stability testing of the perovskite solar cells with shelf lifetime under ambient conditions improved by a factor of more than 4, from ～40 h to ～200 h, using PCBB-2CN-2C8 as the TiO2 modification layer. This work offers not only a promising material for cathode interface engineering, but also provides a viable approach to address the challenges of deep trap states on TiO2 surface in planar perovskite solar cells.
- Li, Yaowen,Zhao, Yue,Chen, Qi,Yang, Yang (Michael),Liu, Yongsheng,Hong, Ziruo,Liu, Zonghao,Hsieh, Yao-Tsung,Meng, Lei,Li, Yongfang,Yang, Yang
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Read Online
- α-D-Mannoside ligands with a valency ranging from one to three: Synthesis and hemagglutination inhibitory properties
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Six mono-, di-, and trivalent α-D-mannopyranosyl conjugates built on aromatic scaffolds were synthesized in excellent yields by Cu(I) catalyzed azide-alkyne cycloaddition reaction (CuAAC). These conjugates were designed to have unique, flexible tails that combine a mid-tail triazole ring, to interact with the tyrosine gate, with a terminal phenyl group armed with benzylic hydroxyl groups to avoid solubility problems as well as to provide options to connect to other supports. Biological evaluation of the prepared conjugates in hemagglutination inhibition (HAI) assay revealed that potency increases with valency and the trivalent ligand 6d (HAI = 0.005 mM) is approximately sevenfold better than the best meta-oriented monovalent analogues 2d and 4d (HAI ≈ 0.033 mM) and so may serve as a good starting point to find new lead ligands.
- Al-Mughaid, Hussein,Khazaaleh, Maha
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- Molecular Scaffolds as Double-Targeting Agents For the Diagnosis and Treatment of Neuroblastoma
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The selective delivery of therapeutic and imaging agents to tumoral cells has been postulated as one of the most important challenges in the nanomedicine field. Meta-iodobenzilguanidine (MIBG) is widely used for the diagnosis of neuroblastoma (NB) due to its strong affinity for the norepinephrine transporter (NET), usually overexpressed on the membrane of malignant cells. Herein, a family of novel Y-shaped scaffolds has been synthesized, which have structural analogues of MIBG covalently attached at each end of the Y-structure. The cellular uptake capacity of these double-targeting ligands has been evaluated in vitro and in vivo, yielding one specific Y-shaped structure that is able to be engulfed by the malignant cells, and accumulates in the tumoral tissue, at significantly higher levels than the structure containing only one single targeting agent. This Y-shaped ligand can provide a powerful tool for the current treatment and diagnosis of this disease.
- Villaverde, Gonzalo,Alfranca, Arantzazu,Gonzalez-Murillo, áfrica,Melen, Gustavo J.,Castillo, Rafael R.,Ramírez, Manuel,Baeza, Alejandro,Vallet-Regí, María
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supporting information
p. 3067 - 3072
(2019/01/14)
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- LIGANDS FOR ENHANCED IMAGING AND DRUG DELIVERY TO NEUROBLASTOMA CELLS
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The present invention concerns aminobenzylguanidine derivative ligands specifically targeting neuroblastoma cells with an improved cellular uptake. The improved cellular uptake provides for the therapeutic and diagnostic use of the ligands in neuroblastoma-related diseases.
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(2019/10/23)
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- Molecular Swings as Highly Active Ion Transporters
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Ions are transported across membrane mostly via carrier or channel mechanisms. Herein, a unique class of molecular-machine-inspired membrane transporters, termed molecular swings is reported that utilize a previously unexplored swing mechanism for promoting ion transport in a highly efficient manner. In particular, the molecular swing, which carries a 15-crown-5 unit as the ion-binding and transporting unit, exhibits extremely high ion-transport activities with EC50 values of 46 nm (a channel:lipid molar ratio of 1:4800 or 0.021 mol % relative to lipid) and 110 nm for K+ and Na+ ions, respectively. Remarkably, such ion transport activities remain high in a cholesterol-rich environment, with EC50 values of 130 (0.045 mol % relative to lipid/cholesterol) and 326 nm for K+ and Na+ ions, respectively.
- Ren, Changliang,Chen, Feng,Ye, Ruijuan,Ong, Yong Siang,Lu, Hongfang,Lee, Su Seong,Ying, Jackie Y.,Zeng, Huaqiang
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supporting information
p. 8034 - 8038
(2019/05/16)
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- Synthesis of novel 1,2,3-triazole based polycarboxylic acid functionalised ligands for MOF systems
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Copper catalysed click reactions are excellent tools to generate various 1,2,3-triazole linked polytopic aromatic carboxylates. The general reaction route involves protection of the carboxylates before proceeding with the click reaction. These polycarboxylate azoles are conveniently prepared for potential utility as novel key building blocks for metal organic frameworks. In one case, the ligand crystallises into a solid structure containing 1D, 2D and 3D features, based on a zigzag 1D structure, a ‘chicken mesh’-like 2D structure and a 3D structure with very well-defined channels.
- Belay, Yonas,Coetzee, Louis-Charl,Williams, D. Bradley G.,Muller, Alfred
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supporting information
p. 501 - 503
(2019/01/14)
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- Aromatic dicarboxylic acid ionic liquid, as well as preparation method and application thereof
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The invention provides an aromatic dicarboxylic acid ionic liquid, as well as a preparation method and application thereof. The ionic liquid has a structure as shown in a general formula (I), whereinR1, R2, R3 and R4 are independently and respectively selected from alkyl having carbon atom number of 1-18, and n is an arbitrary integer of 2-12. Due to the intense adsorption effect of two polar carboxyl (-COO-) and introduction of rigid benzene ring, the ionic liquid can form a firm and orderly physical adsorption protective film on the surface of a metal friction pair in the friction process and has excellent friction reduction and abrasion resistance. Furthermore, the aromatic dicarboxylic acid ionic liquid has relatively ideal thermal stability and the highest decomposition temperature of 205 DEG C.
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Paragraph 0030; 0031; 0039; 0047
(2019/04/06)
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- A polystyrene supported [PdCl-(SeCSe)] complex: A novel, reusable and robust heterogeneous catalyst for the Sonogashira synthesis of 1,2-disubstituted alkynes and 1,3-enynes
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3,5-Bis((phenylselanyl)methyl)phenol has been synthesized as a novel SeCSe pincer type pre-ligand from commercially available 5-hydroxy isophthalic acid through a multistep synthesis. Then, a polystyrene-supported SeCSe pincer ligand and its corresponding palladium complex were prepared and characterized using different techniques including FT-IR, SEM/EDX, TG/DTG, and XPS. The amount of palladium incorporated into the polymer matrix as determined by ICP analysis was obtained to be 3.64 wt% (0.34 mmol g-1). The PS[PdCl-SeCSe] catalytic activity has been evaluated in the Sonogashira coupling of diverse aryl halides with aromatic and aliphatic terminal alkynes. It was also noted that less reactive and inexpensive aryl bromides and aryl chlorides have been successfully cross-coupled with terminal alkynes using low catalyst loading. Moreover, the developed methodology is effective for the stereoselective preparation of substituted 1,3-enynes.
- Mohammadi, Elmira,Movassagh, Barahman
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p. 11471 - 11479
(2018/07/25)
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- Linker functionalisation triggers an alternative 3D-topology for Zn-isophthalate-4,4′-bipyridine frameworks
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A series of four Zn2+ metal-organic frameworks containing functionalised isophthalate linkers and 4,4′-bipyridine pillars have been prepared and characterised. Isophthalates which contain -OC3H2n+1 alkoxy side chains (with n = 1, 2 or 3) form frameworks with a 3D pillared-layer topology instead of the typical 2D layer topology of the renowned coordination polymers with an interdigitated structure (CIDs), which is found for shorter -OC2H5 side chains. The gas adsorption properties of the materials were analysed using N2, CO2 and O2 adsorption measurements at low temperatures.
- Schneemann, Andreas,Rudolf, Robin,Henke, Sebastian,Takahashi, Yukiko,Banh, Hung,Hante, Inke,Schneider, Christian,Noro, Shin-Ichiro,Fischer, Roland A.
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supporting information
p. 8198 - 8203
(2017/07/10)
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- Electrocatalytic Z → E Isomerization of Azobenzenes
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A variety of azobenzenes were synthesized to study the behavior of their E and Z isomers upon electrochemical reduction. Our results show that the radical anion of the Z isomer is able to rapidly isomerize to the corresponding E configured counterpart with a dramatically enhanced rate as compared to the neutral species. Due to a subsequent electron transfer from the formed E radical anion to the neutral Z starting material the overall transformation is catalytic in electrons; i.e., a substoichiometric amount of reduced species can isomerize the entire mixture. This pathway greatly increases the efficiency of (photo) switching while also allowing one to reach photostationary state compositions that are not restricted to the spectral separation of the individual azobenzene isomers and their quantum yields. In addition, activating this radical isomerization pathway with photoelectron transfer agents allows us to override the intrinsic properties of an azobenzene species by triggering the reverse isomerization direction (Z → E) by the same wavelength of light, which normally triggers E → Z isomerization. The behavior we report appears to be general, implying that the metastable isomer of a photoswitch can be isomerized to the more stable one catalytically upon reduction, permitting the optimization of azobenzene switching in new as well as indirect ways.
- Goulet-Hanssens, Alexis,Utecht, Manuel,Mutruc, Dragos,Titov, Evgenii,Schwarz, Jutta,Grubert, Lutz,Bléger, David,Saalfrank, Peter,Hecht, Stefan
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supporting information
p. 335 - 341
(2017/05/16)
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- Assembly and inhibitory activity of monovalent mannosides terminated with aromatic methyl esters: The effect of naphthyl groups
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A series of monovalent α-D-mannoside ligands terminated with aromatic methyl esters have been synthesized in excellent yields using the Cu(I) catalyzed azide-alkyne 1,3-dipolar cycloaddition (“click chemistry”). These mannosides were designed to have a unique aglycone moiety (tail) that combines a triazole ring attached to aromatic methyl esters via a six carbon alkyl chain. The mannose unit of these ligands was linked at the ortho, meta, and para positions of substituted methyl benzoates and 1-, 3-, and 6-substituted methyl 2-napthaoates. In hemagglutination assays, ligands (32A-38A) showed better inhibitory activities than the standard inhibitor, methyl α-D-mannopyranoside. Overall, the naphthyl-based mannoside ligand (37A) showed the best activity and therefore merits further development.
- Al-Mughaid, Hussein,Al-Zoubi, Raed M.,Khazaaleh, Maha,Grindley, T. Bruce
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- Ruthenium-Catalyzed Hydroarylation and One-Pot Twofold Unsymmetrical C?H Functionalization of Arenes
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A methyl phenyl sulfoximine (MPS) is used as a directing group in the ruthenium-catalyzed intramolecular hydroarylation of alkene-tethered benzoic acid derivatives to afford dihydrobenzofurans and indolines in good to excellent yields. A one-pot, unsymmetrical, twofold C?H functionalization involving intramolecular C?C and intermolecular C?C/C?N bond formations is successfully demonstrated by using a single set of catalytic reaction conditions, which is unprecedented thus far. A novel isoquinolone-bearing dihydrobenzofuran is constructed through an unsymmetrical twofold C?H functionalization.
- Ghosh, Koushik,Ramesh, E.,Rit, Raja K.,Sahoo, Akhila K.
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supporting information
p. 7821 - 7825
(2016/07/07)
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- DIFUNCTIONAL MONOMER COMPOUNDS CONTAINING CLICKABLE PENDANT FURYL GROUP AND POLYMERS THEREFROM
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The present invention discloses novel difunctional monomers compound containing pendant clickable furyl group of formula (I), process for the preparation and polymers prepared there from Formula (I) wherein, X is selected from –COOCH3, -COOH, -CON3, -NCO, –CONHNH2, –CH2OH n is selected from 2 to 12.
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Page/Page column 10; 11
(2016/07/05)
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- Carbonaceous borane organic matter and neutron radiation protective material polyester and its preparation (by machine translation)
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This invention proposes a kind of organic matter containing carborane of 5 - (O-carborane -1 ˊ- asian methoxy ) dimethyl isophthalate, and to use this compound preparation of neutron radiation protective material, the material is a polyethylene terephthalate, its structural formula is: In the formula, n=1-200, m=1-200, k=1-6. The carborane structure of the present invention introduced through the chemical bond in the structure of the pendant group of polyester main chain, by selecting different k value of the boron-containing dicarboxylic acid structure of the monomer, the polymerization process in order to control n, m size, in order to obtain a different amount of boron-containing fiber-forming properties of a polymer polyester slice, by direct melting spinning, with different mechanical performance and thermal performance of the hybridization of different organic boron PET fiber. (by machine translation)
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Paragraph 0057; 0058; 0059; 0060
(2016/10/10)
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- Tuning the adsorption behaviors of water, methanol, and ethanol in a porous material by varying the flexibility of substituted groups
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Exploring the adsorption and separation of water, methanol, and ethanol is important concerning the use of a sustainable energy source from biofuel. In this paper, the effects of the flexibility of substituted groups have been studied based on three iso-reticular metal-organic frameworks (MOFs), in which the pore surface is decorated with propargyl (-CH2-C≡CH), allyl (-CH2-CH=CH2), and propyl (-CH2-CH2-CH3) groups respectively. These substituted groups stretch into the channel, acting as gates, and the gate-opening for guests is controlled by the flexibility as well as host-guest interactions. Our study results indicate that (i) the adsorption capacity of water, methanol and ethanol enhances accordingly with the increase of the flexibility of substituted groups; (ii) the adsorptive discrimination of water, methanol, and ethanol on this porous sorbent could be tuned by varying the substituted groups.
- Sha, Yunfei,Bai, Shizhe,Lou, Jiaying,Wu, Da,Liu, Baizhan,Ling, Yun
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supporting information
p. 7235 - 7239
(2016/06/01)
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- DIPICOLYLAMINE DERIVATIVES AND THEIR PHARMACEUTICAL USES
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Dipicolylamine compounds of Formula (I) set forth herein. Also disclosed are pharmaceutical compositions containing metal ions and these compounds. Further disclosed is a method for treating a condition associated with cells containing inside-out phosphatidylserine, with these compounds.
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Paragraph 0043-0045
(2015/12/07)
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- HYDROXY ALIPHATIC SUBSTITUTED PHENYL AMINOALKYL ETHER DERIVATIVES
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New hydroxy aliphatic substituted phenyl aminoalkyl ether compounds of formula (I), compositions thereof and their use as a medicament in the treatment of nervous system diseases and/or the treatment of developmental, behavioral and/or mental disorders associated with cognitive deficits.
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Paragraph 0403-0405; 0449-0451
(2015/12/24)
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- A Modular Synthesis of Multidentate S-, N- and O-Containing Meta- and Paracyclophanes
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The development of a modular approach to macrocycle assembly has enabled the synthesis of a library of pyridine-based macrocycles possessing multiple donor sites where chirality was readily introduced from (R)- or (S)-alanine, a representative amino acid. The facile, regioselective, nucleophilic ring opening of aziridines by dithiols enabled the synthesis of thioether-based linkers which on subsequent alkylation provided access to optically pure macrocycles. A modular approach to macrocyclic assembly has enabled the synthesis of a library of macrocycles possessing multiple donor sites where chirality was readily introduced from (S)-alanine. Key to this approach was the facile, regioselective, nucleophilic ring opening of aziridines by dithiols followed by macrocylisation under conditions of high dilution.
- Rasheed, Omer K.,Bailey, Patrick D.,Lawrence, Amy,Quayle, Peter,Raftery, James
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supporting information
p. 6988 - 6993
(2015/11/16)
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- Unique tetrameric and hexameric mannoside clusters prepared by click chemistry
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The synthesis of novel tetrameric and hexameric mannoside clusters bearing 1,2,3-trizole linkages via Cu(I)-catalyzed azide-alkyne cycloaddition reaction ("click chemistry") is described. An attractive feature of these multiarmed mannoside clusters as potential inhibitors of uropathogenic Escherichia coli is the use of an aglycone whose length is designed to fit in the tyrosine gate. The acetylated mannosides were deprotected and the corresponding de-O-acetylated mannosides were found to exhibit good water solubility.
- Al-Mughaid, Hussein,Al-Zoubi, Raed M.,Paul, Nawal K.,Grindley, T. Bruce
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- Hydroxy aliphatic substituted phenyl aminoalkyl ether derivatives
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New hydroxy aliphatic substituted phenyl aminoalkyl ether compounds of formula (1), compositions thereof and their use as a medicament in the treatment of nervous system diseases and/or the treatment of developmental, behavioral and/or mental disorders associated with cognitive deficits.
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(2014/07/08)
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- Synergistic recognition of halide anions and saccharides by oligohydrazide foldamers
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We synthesized and characterized a new kind of hydrazide oligomer that contains two different types of binding moieties for halide anions and saccharides. The addition of either halide anions or saccharides can induce the oligomers to adopt folded conformations. More interestingly, the oligomers are able to complex both chloride anions and saccharides in the cavity at the same time, implying a synergistic molecular recognition. Benzoylbenzohydrazide oligomers containing two different types of binding moieties could be induced to adopt folded conformations by halide anions and saccharides. Moreover, the oligomers could synergistically host these two different kinds of guests in the cavity. Copyright
- Bie, Fusheng,Wang, Ying,Shang, Jie,Gallagher, Nolan M.,Jiang, Hua
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p. 8135 - 8144
(2014/01/06)
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- Birch Reductive Alkylation of Methyl m-(Hydroxymethyl)benzoate Derivatives and the Behavior of o- and p-(Hydroxymethyl)benzoates under Reductive Alkylation Conditions
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Birch reductive alkylation of methyl m-(hydroxymethyl)benzoate derivatives, using lithium in ammonia-tetrahydrofuran in the presence of tertbutyl alcohol, can be achieved without significant loss of benzylic oxygen substituents. Similar treatment of o- and p-(hydroxymethyl)benzoate derivatives results largely in loss of benzylic oxygen substituents. The results are rationalized by computations describing electron density patterns in the putative radical anion intermediate involved in these reactions.
- Fretz, Samuel J.,Hadad, Christopher M.,Hart, David J.,Vyas, Shubham,Yang, Dexi
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supporting information
p. 83 - 92
(2013/03/29)
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- A selective turn-on fluorescent sensor for sulfur mustard simulants
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A fluorescent turn-on sensor for the selective and sensitive detection of sulfur mustard simulants in water that uses a metal-ion indicator displacement assay (IDA) has been devised. In this IDA approach, a sulfur mustard simulant (the analyte) is allowed to react with a dithiol (1) to form a podand (2). This podand has a strong affinity to bind with Cd2+ and displaces an indicator (4-methylesculetin, ME) from a Cd2+-indicator complex (8) to give a turn-on of fluorescence. The detection is rapid and highly selective, as we did not observe any interference from other electrophiles, even from the oxygen analogue of the mustard simulant. The protocol was successfully used for the detection of the simulant present on surfaces and in soil samples.
- Kumar, Vinod,Anslyn, Eric V.
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p. 6338 - 6344
(2013/06/04)
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- Pyridostatin analogues promote telomere dysfunction and long-term growth inhibition in human cancer cells
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The synthesis, biophysical and biological evaluation of a series of G-quadruplex interacting small molecules based on a N,N′-bis(quinolinyl) pyridine-2,6-dicarboxamide scaffold is described. The synthetic analogues were evaluated for their ability to stabilize telomeric G-quadruplex DNA, some of which showed very high stabilization potential associated with high selectivity over double-stranded DNA. The compounds exhibited growth arrest of cancer cells with detectable selectivity over normal cells. Long-time growth arrest was accompanied by senescence, where telomeric dysfunction is a predominant mechanism together with the accumulation of restricted DNA damage sites in the genome. Our data emphasize the potential of a senescence-mediated anticancer therapy through the use of G-quadruplex targeting small molecules based on the molecular framework of pyridostatin.
- Müller, Sebastian,Sanders, Deborah A.,Di Antonio, Marco,Matsis, Stephanos,Riou, Jean-Fran?ois,Rodriguez, Rapha?l,Balasubramanian, Shankar
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supporting information; experimental part
p. 6537 - 6546
(2012/09/08)
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- Synthesis, characterization, and in vitro testing of a bacteria-targeted MR contrast agent
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A bacteria-targeted MR contrast agent, Zn-1, consisting of two Zn-dipicolylamine (Zn-dpa) groups conjugated to a GdIII chelate has been synthesized and characterized. In vitro studies with S. aureus and E. coli show that Zn-1 exhibits a significant improvement in bacteria labeling efficiency vs. control. Studies with a structural analogue, Zn-2, indicate that removal of one Zn-dpa moiety dramatically reduces the agent's affinity for bacteria. The ability of Zn-1 to significantly reduce the T1 of labeled vs. unlabeled bacteria, resulting in enhanced MR image contrast, demonstrates its potential for visualizing bacterial infections in vivo. A bacteria-targeted MR contrast agent consisting of two Zn-dipicolylamine (Zn-dpa) groups conjugated to a Gd(III) chelate has been synthesized and characterized. This contrast agent significantly reduces the T1 of labeled versus unlabeled bacteria, resulting in enhanced MR image contrast, demonstrating its potential for visualizing bacterial infections in vivo. Copyright
- Matosziuk, Lauren M.,Harney, Allison S.,MacRenaris, Keith W.,Meade, Thomas J.
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scheme or table
p. 2099 - 2107
(2012/06/15)
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- FLUORINATED AROMATIC BIS(ACYL)-CONTAINING COMPOUNDS AND POLYESTERS PREPARED THEREFROM
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A fluorinated bis(acyl)-containing compound of Formula (I), where R1, Ar, L, R2, R3, Rf, n, p and q are as defined in the claims, and a fluorinated polyester formed from the fluorinated bis(acyl) compound are described. More particularly, the fluorinated bis(acyl) has an aromatic ring bonded to two acyl groups plus at least one third group that contains a perfluoroalkylsulfonamido group. The fluorinated polyesters formed from the fluorinated bis(acyl)-containing compound can be used to provide a low energy surface with a relatively low refractive index compared to many other polyesters. A method of preparing a monosubstituted-arylene compound of formula Rf1-L2 -CH2-Ar2-CH2-W, where Ar2, Rf1, L2, R6 and W are as defined in the claims by reaction of a compound of formula Rf1-L2-H with a compound of formula W-CH2-Ar2-CH2-W.
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(2011/02/24)
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- Novel photo-cross-linkable dendrimers having thermal de-cross-linking properties
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Novel poly(aryl ether) type dendrimers having photo-cross-linking and thermal de-cross-linking properties were synthesized by a convergent method. A protected A2B monomer, 1-allyloxy-3,5-bis(bromomethyl)benzene, was newly prepared for the dendrimer synthesis. Palladium-catalyzed deprotection of an allyl group proceeded in high yields. The films of dendrimers containing a photoacid generator (PAG) became insoluble in solvents on irradiation. The irradiated films became soluble in solvents after baking at 120-200°C. The insolubilization and redissolution profiles were strongly affected by irradiation and baking conditions and the generation of the dendrimers. A reaction pathway was studied by TGA and DTA analysis and FT-IR spectroscopy.
- Okamura, Haruyuki,Shirai, Masamitsu
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scheme or table
p. 5087 - 5094
(2011/11/29)
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- Direct synthesis of terminally "Clickable" linear and hyperbranched polyesters
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1,3-Dipolar cycloaddition of an organic azide and an acetylenic unit, often referred to as the "click reaction", has become an important ligation tool both in the context of materials chemistry and biology. Thus, development of simple approaches to directly generate polymers that bear either an azide or an alkyne unit has gained considerable importance. We describe here a straightforward approach to directly prepare linear and hyperbranched polyesters that carry terminal propargyl groups. To achieve the former, we designed an ABtype monomer that carries a hydroxyl group and a propargyl ester, which upon self-condensation under standard transesterification conditions yielded a polyester that carries a single propargyl group at one of its chain-ends. Similarly, an AB2 type monomer that carries one hydroxyl group and two propargyl ester groups, when polymerized under the same conditions yielded a hyperbranched polymer with numerous "clickable" propargyl groups at its molecular periphery. These propargyl groups can be readily clicked with different organic azides, such as benzyl azide, ω-azido heptaethyleneglycol monomethylether or 9-azidomethyl anthracene. When an anthracene chromophore is clicked, the molecular weight of the linear polyester could be readily estimated using both UV-visible and fluorescence spectroscopic measurements. Furthermore, the reactive propargyl end group could also provide an opportunity to prepare block copolymers in the case of linear polyesters and to generate nanodimensional scaffolds to anchor a variety of functional units, in the case of the hyperbranched polymer.
- Ramkumar,Amala Rose,Ramakrishnan
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experimental part
p. 3200 - 3209
(2011/04/18)
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- Jacketed polymers with dendritic carbazole side groups and their applications in blue light-emitting diodes
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Styrene-based monomers with the first- and second-generation dendronized carbazoles were synthesized by a convergent strategy. Conventional free radical polymerizations were carried out to synthesize the dendronized jacketed polymers using these two monomers. The apparent molecular weights of the two polymers determined by gel permeation chromatography were 57 000 and 34 000 g/mol, respectively. The polymers had excellent thermal stability with their 5% weight loss temperatures all above 360 °C. Their photophysical properties in solutions and films were investigated. Different solvents had negligible effects on their UV-vis or photoluminescent (PL) spectra. A 10 nm blue shift of the emission peak was observed in the PL spectra of films compared with those of solutions. After the films were annealed, the emission peaks became narrower. X-ray diffraction techniques were utilized to examine the phase structures of the dendronized jacketed polymers. The first-generation polymer formed a hexatic columnar nematic phase, while the second-generation one exhibited a columnar nematic phase. This stiff main-chain conformation and the dendritic side-group structure could reduce the intramolecular interactions and aggregations of the carbazole side groups and prevent the formation of excimers, which would be beneficial to the optoelectronic properties. The two polymers showed similar electrochemical properties. Their HOMO levels were about -5.3 eV, which was quite close to that of PEDOT:PSS. Electroluminescent (EL) devices were fabricated in two configurations. A new emission peak was found in the EL spectra compared with the PL spectra. All the devices emitted blue lights and possessed low driving voltages. An introduction of an electron-transporting layer could greatly improve the device properties. The best device could reach a luminescence of 2195 cd/m2, a current efficiency of 0.240 cd/A, and an external quantum efficiency of 0.353%.
- Jin, Hao,Xu, Yiding,Shen, Zhihao,Zou, Dechun,Wang, Dan,Zhang, Wei,Fan, Xinghe,Zhou, Qifeng
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experimental part
p. 8468 - 8478
(2011/11/12)
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- A new thermo- and photo-driven [2]rotaxane
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A new rotaxane with functional chromophores porphyrin and fluorene as stoppers has been synthesized. It displays dual fluorescent character. The macrocycle ring can shuttle between the fumaramide part and the succinimide part on the dumbbell. Heating and UV light irradiating on the rotaxane lead to the reversible E/Z conversion, driving the ring to shuttle between the two stations. The optical properties of porphyrin and fluorene stoppers of the thread do not change so much while the ring shuttles because the macrocycle does not interact with the two stoppers. However, the active group, propargyloxyl, is introduced onto the two sides of the ring so that the rotaxane has the potential to be functionalized by further decoration.
- Ji, Feng-Yuan,Zhu, Liang-Liang,Ma, Xiang,Wang, Qiao-Chun,Tian, He
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supporting information; experimental part
p. 597 - 600
(2009/05/27)
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- De novo Design and synthesis of N-benzylanilines as new candidates for VEGFR tyrosine kinase inhibitors
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N-Benzylanilines were designed and synthesized as vascular endothelial growth factor (VEGF)-2 inhibitors using de novo drug design systems based on the X-ray structure of VEGFR-2 kinase domain. Among compounds synthesized, compound 3 showed the most potent inhibitory activity toward VEGFR-2 (KDR) tyrosine kinase and its IC50 value was 0.57 μM.
- Uno, Masaharu,Ban, Hyun Seung,Nabeyama, Wataru,Nakamura, Hiroyuki
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scheme or table
p. 979 - 981
(2009/02/05)
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- A redox-switchable α-cyclodextrin-based [2]rotaxane
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A bistable [2]rotaxane comprising an α-cyclodextrin (α-CD) ring and a dumbbell component containing a redox-active tetrathiafulvalene (TTF) ring system within its rod section has been synthesized using the Cu(I)-catalyzed azide-alkyne cycloaddition, and the redox-driven movements of the α-CD ring between the TTF and newly formed triazole ring systems have been elucidated. Microcalorimetric titrations on model complexes suggested that the α-CD ring prefers to reside on the TTF rather than on the triazole ring system by at least an order of magnitude. The fact that this situation does pertain in the bistable [2]rotaxane has not only been established quantitatively by electrochemical experiments and backed up by spectroscopic and chiroptical measurements but also been confirmed semiquantitatively by the recording of numerous cyclic voltammograms which point, along with the use of redox-active chemical reagents, to a mechanism of switching that involves the oxidation of the neutral TTF ring system to either its radical cationic (TTF?+) or dicationic (TTF2+) counterparts, whereupon the α-CD ring, moves along the dumbbell to encircle the triazole ring system. Since redox control by both chemical and electrochemical means is reversible, the switching by the bistable [2]rotaxane can be reversed on reduction of the TTF?+ or TTF2+ back to being a neutral TTF. Copyright
- Zhao, Yan-Li,Dichtel, William R.,Trabolsi, Ali,Saha, Sourav,Aprahamian, Ivan,Stoddart, J. Fraser
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supporting information; experimental part
p. 11294 - 11296
(2009/02/05)
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- Recognition of solvent exposed protein surfaces using anthracene derived receptors
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A new class of receptor is described that can selectively bind to the solvent exposed surface of proteins such as cytochrome c and lysozyme with low micromolar affinity over cytochrome c551, α-lactalbumin, myoglobin and RNase A, under physiologically relevant conditions (5 mM phosphate, pH 7.4). The use of anthracene as a hydrophobic scaffold allows the receptor to act as a selective chemosensor via fluorescence quenching or FRET. The study reveals that co-operative electrostatic interactions over a large surface area dominate binding. Further investigations reveal that the receptor binds to the solvent exposed heme edge of cytochrome c inhibiting its reaction with small reducing agents and validating the strategy for the disruption of protein function. This journal is The Royal Society of Chemistry.
- Wilson, Andrew J.,Hong, Jason,Fletcher, Steven,Hamilton, Andrew D.
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p. 276 - 285
(2008/03/28)
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- A novel amphiphilic Re1 complex with bis(fullerene)-substituted bipyridine ligands: Synthesis, electrochemistry, and langmuir film
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An amphiphilic fullerene (C60) derivative with a (bipyridine)-tricarbonylrhenium(I) chloride polar head group has been prepared. Electrochemical studies indicate that some ground state electronic interactions between the fullerene subunit and the metal complexed moiety are present in ReI complex 1. The Langmuir film of this compound has been characterized by its surface pressure versus molecular area isotherm and Brewster angle microscopy (BAM) observations. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
- Hwi, Deuk Lee,Sang, Keun Oh,Chan, Soo Choi,Kay, Kwang-Yol
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p. 503 - 508
(2008/09/20)
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- Anion templated surface assembly of a redox-active sensory rotaxane
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Anion templation is used to assemble novel redox-active bis-ferrocene functionalised rotaxane self-assembled monolayers (SAMs) on to gold electrode surfaces; after template removal, the unique SAM rotaxane binding domain is capable of selectively sensing chloride ions electrochemically. The Royal Society of Chemistry.
- Bayly, Simon R.,Gray, Thomas M.,Chmielewski, Michal J.,Davis, Jason J.,Beer, Paul D.
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p. 2234 - 2236
(2007/12/27)
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- A simple and effective method for chemoselective esterification of phenolic acids
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A new method for efficient and chemoselective esterification of phenolic acids in KHCO3/alkyl halide/DMF reaction system is described, by which a series of phenoic acid esters were obtained in excellent yields.
- Guo, Wei,Li, Junfei,Fan, Ningjuan,Wu, Weiwei,Zhou, Peiwen,Xia, Chizhong
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p. 145 - 152
(2007/10/03)
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- NEW ISOBENZOXAZINONES AND THEIR USE AS ULTRAVIOLET LIGHT ABSORBERS
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The present invention relates to new substituted isobenzoxazinones, in particular of formula (I) as given in claim 1, and their use as ultraviolet light absorbers, in particular for organic polymers.
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Page/Page column 8
(2010/02/15)
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- Organic thiol metal-free stabilizers and plasticizers for halogen-containing polymers
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Organic thiol compounds based on pentaerythritol and dipentaerythritol are described herein. More specifically, the compounds of the present invention are mixed esters of pentaerythritol and dipentaerythritol having at least one sulfhydryl group and preferably a plurality of sulfhydryl groups as well as at least one non-thiol-containing group. The organic thiol compounds are utilized to plasticize and/or heat stabilize halogen-containing polymer compositions especially poly(vinyl chloride) compositions. The compositions are substantially free or free of metal-based stabilizers, Lewis acids and terpenes. The compounds of the present invention are ideally utilized in polymers normally susceptible to deterioration and color change which can occur during processing of the polymer or exposure of the polymer to certain environments and surprisingly also serve as excellent plasticizers.
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Page/Page column 3
(2010/02/11)
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- A novel phthalocyanine with two axial fullerene substituents
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A silicon phthalocyanine with two axial fullerene substituents was synthesized, and its electrochemical, absorption- and film-properties were characterized.
- Kim, Kun Nam,Choi, Chan Soo,Kay, Kwang-Yol
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p. 6791 - 6795
(2007/10/03)
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- COMPOUND HAVING PHOSPHORYLCHOLINE GROUP, POLYMER THEREOF, AND PROCESS FOR PRODUCING THE SAME
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A compound of the invention is a specific compound having a phosphorylcholine group, and a polymer of the invention comprises at least 1 mol% of repeating units with a phosphorylcholine group and has a number-average molecular weight of 1,000 or more, the repeating units with a phosphorylcholine group being represented by the formula (II): wherein A is a bond selected from a single bond, -O-, -COO-, -OOC-, -CONH-, -NH-, -NHCO-, -NR2- and -CH2O- where R2 is an alkyl group having 1 to 6 carbon atoms; and m is an integer of 1 to 12.
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Page/Page column 14
(2010/02/11)
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- Molecular tripods showing fluorescence enhancement upon binding to streptavidin
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(Chemical Equation Presented) We introduce a new approach to biotin-streptavidin assays based on a molecular tripod which consists of biotin, a fluorophore, and a quencher. The interaction between streptavidin and molecular tripods perturbs the ground-state quencher-fluorophore dimeric conformation in the absence of streptavidin and diminishes the intrinsic self-quenching of a quencher-fluorophore pair. The emission intensity of the molecular tripods plus streptavidin is 3.5-5.2 times that of molecular tripods in the absence of streptavidin.
- Tae, Woo Kim,Hey, Young Yoon,Park, Jung-Hyun,Kwon, Oh-Hoon,Jang, Du-Jeon,Hong, Jong-In
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p. 111 - 114
(2007/10/03)
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- A simple deprotection of triflate esters of phenol derivatives
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Efficient conversion of aryl triflates into the corresponding phenols has been accomplished with Et4NOH. In contrast to other cleavage reactions, such functional groups as nitro, ketone, halogen, amide and sulfonamide groups were intact under the reaction conditions. This mild removal of the trifluoromethanesulfonyl group would serve a new protecting group of phenols.
- Ohgiya, Tadaaki,Nishiyama, Shigeru
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p. 6317 - 6320
(2007/10/03)
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- Poly(ethylene glycol)-supported nitroxyls: Branched catalysts for the selective oxidation of alcohols
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Nitroxyl radicals such as 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) are highly selective oxidation catalysts for the conversion of primary alcohols into the corresponding aldehydes. In this study, direct tethering of TEMPO units onto linear poly(ethylene glycol) (PEG) has afforded macromolecular catalysts that exhibit solubility in both aqueous and organic solvents. Recovery of the dissolved polymer-supported catalyst has been carried out by precipitation with a suitable solvent such as diethyl ether. The high catalyst activities and selectivities associated traditionally with nitroxyl-mediated oxidations of alcohols are retained by the series of "linker-less" linear PEG-TEMPO catalysts in which the TEMPO moiety is coupled directly to the PEG support. Although the selectivity remains unaltered, upon recycling of the linker-less polymer-supported catalysts, extended reaction times are required to maintain high yields of the desired carbonyl compounds. Alternatively, attachment of two nitroxyl radicals onto each functionalized PEG chain terminus via a 5-hydroxyisophthalic acid linker affords branched polymer-supported catalysts. In stark contrast to the linker-less catalysts, these branched nitroxyls exhibit catalytic activities up to five times greater than 4-methoxy-TEMPO alone under similar conditions. In addition, minimal decrease in catalytic activity is observed upon recycling of these branched macromolecular catalysts via solvent-induced precipitation. The high catalytic activities and preservation of activity upon recycling of these branched systems is attributed to enhanced regeneration of the nitroxyl species as a result of intramolecular syn-proportionation.
- Ferreira, Pedro,Phillips, Emyr,Rippon, David,Shik, Chi Tsang,Hayes, Wayne
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p. 6851 - 6859
(2007/10/03)
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- Vitamin D analogues
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The invention concerns novel bi-aromatic compounds having the formula: which are analogs of vitamin D, the process of preparing them, as well as their use in pharmaceutical compositions in human or veterinary medicine, particularly in dermatology, cancer treatment, treatment of auto-immune diseases, and in organ or tissue transplants. Cosmetic compositions and methods of use are also included.
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Page column 12
(2010/02/05)
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- Nonplanar aromatic compounds. 8.1 synthesis, crystal structures, and aromaticity investigations of the 1,n-dioxa[n](2,7)pyrenophanes. How does bending affect the cyclic π-electron delocalization of the pyrene system?
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A series of 1,n-dioxa[n](2,7)pyrenophanes (n = 7-12) with increasingly nonplanar pyrene moieties was synthesized by a 9-10 step sequence starting from 5-hydroxyisophthalic acid. The crystal structure of each member of this series was determined crystallographically. Several spectroscopic properties were found to vary with the extent of the nonplanarity of the pyrene unit. The way in which the distortion from planarity of the pyrene system influences its π-electron delocalization was investigated by using two quantitative descriptors of aromaticity based on geometry (HOMA) and magnetism (magnetic susceptibility and NICS). Both methods suggest that the aromaticity of the pyrene moiety is diminished only slightly upon increasing the bend angle θ from 0° to 109.2°.
- Bodwell, Graham J.,Bridson, John N.,Cyranski, Michal K.,Kennedy, Jason W. J.,Krygowski, Tadeusz M.,Mannion, Michael R.,Miller, David O.
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p. 2089 - 2098
(2007/10/03)
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