- Synthesis and self-assembly behaviours of side-chain smectic thiol-ene polymers based on the polysiloxane backbone
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A series of polysiloxane side chain liquid crystal polymers (PSCLCPs) with chiral and achiral substitutions in the side chains, denoted as PMMS-Xchol-n (n = 0, 0.1, 0.15, 0.2, 0.3, 0.4, 0.5 0.6, 0.7. 0.8, 0.9, and 1.0, respectively, the molar content of the chiral cholesteric unit (Xchol) in a specific polymer), were successfully synthesized via thiol-ene click chemistry. The molecular structures of the polymers were confirmed by 1H-NMR, FT-IR, gel permeation chromatography (GPC) and thermogravimetric analysis (TGA). Their liquid crystalline (LC) properties and self-assembling behaviors were investigated in detail by a combination of various techniques, such as differential scanning calorimetry (DSC), polarized optical microscopy (POM), and X-ray diffraction. The results demonstrated that the phase transition behaviour and the self-assembly structure of the polymers were significantly influenced by Xchol and temperatures. With increased Xchol, the clearing points increased significantly, their mesogenic temperature ranges greatly widened, and abundant mesophases developed. Generally, two different types of LC phase structures and three different molecular arrangements were observed, depending on the two LC building blocks. Polymers with Xchol below 0.3 could self-assemble into a smectic E (SmE)-like structure and a single layer smectic A (SmAs) structure upon heating. When Xchol was between 0.4 and 0.7, a single phase structure of a SmAs or a bilayer smectic A (SmAd) could be observed. While for polymers with Xchol over 0.8, a SmAd phase structure was self-organized, further heating led to a SmAs structure. Moreover, when the molar ratio of the chiral group or achiral group was about 0.1, a microphase-separated smectic morphology could be found, indicating that the introduction of a small amount of any components in the copolymers might destroy the well-ordered structures.
- Yao, Wenhuan,Gao, Yanzi,Yuan, Xiao,He, Baofeng,Yu, Haifeng,Zhang, Lanying,Shen, Zhihao,He, Wanli,Yang, Zhou,Yang, Huai,Yang, Dengke
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- Synthesis of amide-type smectic a side-chain polysiloxane liquid crystal
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In this paper, monomer N-(4-hydroxyphenyl-1) 4-alkyloxybenzamide was obtained by the Williamson reaction, acylation, and aminolysis. Side-chain polysiloxane liquid crystal was then successfully synthesized by a grafting reaction of the monomer. The monomer and liquid crystal were characterized by Fourier-transform infrared spectroscopy, 1H nuclear magnetic resonance spectroscopy, differential scanning calorimetry, and polarization microscopy. The results showed that both monomer and polymer exhibited thermotropic smectic A behavior, and they were very stable within the studied temperature range. They may be very sensitive to both electric and magnetic fields because of their liquid crystalline properties.
- Gao, Jianfeng,Sun, Zhongzhan,Peng, Tao,Yang, Lina
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- Wide-band reflective films produced by side-chain cholesteric liquid-crystalline elastomers derived from a binaphthalene crosslinking agent
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A series of novel side-chain cholesteric liquid-crystalline elastomers based on polysiloxane and cholesterol derivate monomer were prepared by adopting a crosslinking agent containing binaphthalene group. The chemical structures and mesomorphic properties of the monomers and elastomers were confirmed by FT-IR, 1H NMR, DSC and POM measurements. Worthily, the elastomers exhibited unusual temperature dependence of the helical twisting power (HTP) which is demonstrated resulting from coordination of the crosslinking agent and the mesogenic units. With increase in temperature, the HTP of elastomers containing small quantity of the crosslinking unit exhibited a turning point, while that of elastomers comprising much more crosslinking unit shifted straight. Furthermore, a single layer wide-band reflective film with non-uniform pitch distribution was prepared by utilizing the HTP variety of elastomers with change in temperature. From scanning electron microscopy (SEM) investigations, the mechanism of the broadband reflection was verified.
- Wu, Xiaojuan,Yu, Lilong,Cao, Hui,Guo, Renwei,Li, Kexuan,Cheng, Zihui,Wang, Feifei,Yang, Zhou,Yang, Huai
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- A series of novel side chain liquid crystalline polysiloxanes containing cyano- and cholesterol-terminated substituents: Where will the structure-dependence of terminal behavior of the side chain reappear?
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A series of polysiloxane side chain liquid crystal polymers with strong polarity cyano substitution-terminated achiral side chains and cholesterol-terminated chiral side chains was successfully synthesized via thiol-ene click chemistry. 1H-NMR, FT-IR, and thermogravimetric analysis were used to confirm their chemical structures and thermal stabilities. Their phase transition behaviors and phase structures were systematically investigated by a combination of analysis methods such as differential scanning calorimetry, polarized optical microscopy, and X-ray. Results revealed that attributing to the decisive role of the polarity interaction, all the polymers only developed a monolayer interdigitated SmA phase in which the period arrangement was determined by the cyano-terminated side chains, the increased content of cholesterol-terminated chiral side chains (Xchol) just expanded the distance between neighboring molecules within a layer.
- Yao, Wenhuan,Gao, Yanzi,Zhang, Cuihong,Li, Chenyue,Li, Fasheng,Yang, Zhou,Zhang, Lanying
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- Design and phase transition behavior of siloxane-based monomeric and dimeric liquid crystals bearing cholesteryl mesogenic groups
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A series of siloxane-based monomeric and dimeric liquid crystals (LCs) bearing cholesteryl mesogenic groups were newly synthesized and their phase transition behavior was investigated by polarized optical microscopy (POM), differential scanning calorimetry (DSC), and X-ray diffraction (XRD). All the siloxane-based LCs obtained in this study showed a smectic A phase in a wide temperature range. Among the siloxane-based LCs obtained, only the dimeric LC with a shortest siloxane unit at a central part of a spacer was found to exhibit a chiral nematic phase and a blue phase in addition to the smectic A phase. The difference in the thermal properties of the siloxane-based dimeric LCs was investigated in terms of their conformations. Furthermore, the results obtained for the siloxane-based LCs were discussed with comparing with those of homologues having the normal alkyl chains and spacers.
- Katsuki, Kaito,Kaneko, Kosuke,Kaneko, Kimiyoshi,Kato, Riki,Miyamoto, Nobuyoshi,Hanasaki, Tomonori
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- Gas chromatographic separation of structural isomers on cholesteric liquid crystal stationary phase materials
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A new series of liquid crystalline polysiloxanes with a very wide range of mesomorphic temperatures had been prepared. They contained 4-cholesteryl-(10- undecen-1-yloxy)biphenyl-4′-carboxylate mesogenic and 4-biphenyl-4′- allyloxybenzoate mesogenic side groups displaying an enantiotropic cholesteric phases. The mesomorphic polysiloxane specimen with the widest temperature range was used as the stationary phase in a gas chromatography capillary column and it showed high column efficiency and made great promise for the separation of different structure isomer compounds.
- Lee, Yi-Wen,Lin, Chih-Hung
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Read Online
- Full-spectrum selective reflection annular side chain liquid crystal oligomer film and preparation method thereof
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The invention discloses a full-spectrum selective reflection annular side chain liquid crystal oligomer film and a preparation method thereof. The preparation method comprises the following steps: respectively carrying out graft copolymerization on a chiral liquid crystal monomer and an achiral rod-like monomer or two chiral liquid crystal monomers and annular polymethyl hydrogen-containing siloxane to construct the full-spectrum selective reflection annular side chain liquid crystal oligomer film, the structural formula is shown as a formula I. The cyclic side chain liquid crystal oligomer can realize full-spectrum selective reflection in the heating process; at room temperature, the annular side chain liquid crystal oligomer film can realize full-spectrum selective reflection along with the change of an incident angle. The cyclic side chain liquid crystal oligomer prepared by the method has dual characteristics that dynamic full-spectrum selective reflection changes along with temperature and incident angle, and has a wide application prospect in the optical field, the preparation process is safe to operate, and reaction conditions are mild.
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Paragraph 0049; 0054; 0057-0058
(2021/08/06)
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- Epoxy compound, composition, material for semiconductor package, molded product, electrical and electronic device, and semiconductor package
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Epoxy compounds, compositions, materials for semiconductor packages, molded products, electrical and electronic devices, and semiconductor packages are provided. The epoxy compound is represented by the following Chemical Formula 1 and has at least one mesogenic naphthalene unit. In Chemical Formula 1, at least one of M1, M2, or M3, which is a mesogenic unit, is a naphthalene unit. M1, M2, M3, L1, L2, and E1 and E2 are as defined in the detailed description. The chemical formula (1) is E1-M1-L1-M2-L2-M3-E2.
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Paragraph 0191-0196
(2021/05/15)
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- TRUNCATED ITRACONAZOLE ANALOGUES AND METHODS OF USE THEREOF
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Disclosed herein are analogues of itraconazole that are potent hedgehog signaling pathway inhibitors. The compounds are expected to be useful in the treatment of cell proliferation disorders such as cancer, particularly cancers that are dependent upon the hedgehog signaling pathway such as basal cell carcinoma and medulloblastoma.
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Paragraph 0097; 0101
(2021/02/19)
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- 2-Aryl benzazole derived new class of anti-tubercular compounds: Endowed to eradicate mycobacterium tuberculosis in replicating and non-replicating forms
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The high mortality rate and the increasing prevalence of Mtb resistance are the major concerns for the Tuberculosis (TB) treatment in this century. To counteract the prevalence of Mtb resistance, we have synthesized 2-aryl benzazole based dual targeted molecules. Compound 9m and 9n were found to be equally active against replicating and non-replicating form of Mtb (MIC(MABA) 1.98 and 1.66 μg/ml; MIC(LORA) 2.06 and 1.59 μg/ml respectively). They arrested the cell division (replicating Mtb) by inhibiting the GTPase activity of FtsZ with IC50 values 45 and 64 μM respectively. They were also capable of kill Mtb in non-replicating form by inhibiting the biosynthesis of menaquinone which was substantiated by the MenG inhibition (IC50 = 11.62 and 7.49 μM respectively) followed by the Vit-K2 rescue study and ATP production assay.
- Datta, Dhrubajyoti,Debnath, Joy,Franzblau, Scott G.,Ghosh, Kalyan Sundar,Hari, Natarajan,Ma, Rui,Rana, Shiwani,Velappan, Anand Babu
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- Enantioselective Synthesis of 3-Fluorochromanes via Iodine(I)/Iodine(III) Catalysis
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The chromane nucleus is common to a plenum of bioactive small molecules where it is frequently oxidized at position 3. Motivated by the importance of this position in conferring efficacy, and the prominence of bioisosterism in drug discovery, an iodine(I)/iodine(III) catalysis strategy to access enantioenriched 3-fluorochromanes is disclosed (up to 7:93 e.r.). In situ generation of ArIF2 enables the direct fluorocyclization of allyl phenyl ethers to generate novel scaffolds that manifest the stereoelectronic gauche effect. Mechanistic interrogation using deuterated probes confirms a stereospecific process consistent with a type IIinv pathway.
- Daniliuc, Constantin G.,Gilmour, Ryan,Neufeld, Jessica,Sarie, Jér?me C.,Thiehoff, Christian
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p. 15069 - 15075
(2020/06/17)
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- Phosphoramidite containing phenolic hydroxyl, preparation method and application of phosphoramidite
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The invention provides phosphoramidite containing phenolic hydroxyl and a preparation method and application of the phosphoramidite. Specifically, the invention discloses a compound shown as a formulaI, a preparation method of the compound and application of the compound serving as a solid synthesis unit. By utilizing the compound as shown in the formula I, radionuclide can be simply and efficiently labeled on nucleic acids such as aptamers, siRNAs or mRNAs, so that diagnostic reagents and therapeutic drugs are prepared.
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Paragraph 0133-0135
(2020/08/07)
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- Visible-Light-Induced Deoxygenation/Defluorination Protocol for Synthesis of γ,γ-Difluoroallylic Ketones
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Herein, we describe an efficient, practical photocatalytic deoxygenation/defluorination protocol for the synthesis of γ,γ-difluoroallylic ketones from commercially available aromatic carboxylic acids, triphenylphosphine, and α-trifluoromethyl alkenes. The protocol has good functional group tolerance and a broad substrate scope. Using this method, we accomplished the late-stage functionalization of several bioactive molecules.
- Guo, Yuan-Qiang,Wang, Ruiguo,Song, Hongjian,Liu, Yuxiu,Wang, Qingmin
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supporting information
p. 709 - 713
(2020/01/31)
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- Cholesteric fluorescent liquid crystal polysiloxanes with different liquid crystal side chain lengths—Synthesis and properties
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With polymethylhydrogensiloxane (PMHS) as the main chain, two series side-chain cholesteric liquid crystal polymers (ChLCPs) with different liquid crystal side chain lengths were prepared by hydrosilylation reaction. Then two series of cholesteric fluorescent liquid crystal polymers (FL-ChLCPs) were obtained by etherification reaction. The obtained FL-ChLCPs have both excellent mesomorphic behavior, and great photoluminescent property. We confirmed their chemical structures by FT-IR, and 1H NMR spectroscopy, and found them with excellent thermal stability by TGA. We characterized their mesomorphic behavior and thermal performance by POM, DSC and XRD, and confirmed all the polymers belonged to cholesteric phase. FL-ChLCPs emitted different-intensity fluorescence under UV light, and we found some regularity by PL spectrum.
- Cong, Yue-hua,Gao, Shang,He, Xiao-zhi,Jia, Ying-gang,Liu, Ze-ping,Meng, Fan-bao,Zhang, Bao-yan
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- Truncated Itraconazole Analogues Exhibiting Potent Anti-Hedgehog Activity and Improved Drug-like Properties
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We conducted a structure-activity relationship study to explore simplified analogues of the itraconazole (ITZ) scaffold for their ability to inhibit the hedgehog (Hh) signaling pathway. These analogues were based on exploring the effects of chemical modifications to the linker and triazolone/side chain region of ITZ. Analogue 11 was identified as the most potent compound in our first generation, with an IC50 value of 81 nM in a murine Hh-dependent basal cell carcinoma. Metabolic identification studies led us to identify truncated piperazine (26) as the major metabolite in human liver microsomes (HLMs) and an improved Hh pathway inhibitor (IC50 = 22 nM). This work verifies that continued truncation of the ITZ scaffold is a practical method to maintain potent anti-Hh activity while also reducing the molecular weight for the ITZ scaffold and achieving improved pharmacokinetic properties.
- Wen, Jiachen,Chennamadhavuni, Divya,Morel, Shana R.,Hadden, M. Kyle
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supporting information
p. 1290 - 1295
(2019/09/30)
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- Silver(I)-Catalyzed Widely Applicable Aerobic 1,2-Diol Oxidative Cleavage
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The oxidative cleavage of 1,2-diols is a fundamental organic transformation. The stoichiometric oxidants that are still predominantly used for such oxidative cleavage, such as H5IO6, Pb(OAc)4, and KMnO4, generate stoichiometric hazardous waste. Herein, we describe a widely applicable and highly selective silver(I)-catalyzed oxidative cleavage of 1,2-diols that consumes atmospheric oxygen as the sole oxidant, thus serving as a potentially greener alternative to the classical transformations.
- Zhou, Zhong-Zhen,Liu, Mingxin,Lv, Leiyang,Li, Chao-Jun
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supporting information
p. 2616 - 2620
(2018/02/13)
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- An Efficient Aerobic Oxidation Protocol of Aldehydes to Carboxylic Acids in Water Catalyzed by an Inorganic-Ligand-Supported Copper Catalyst
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A method for the aerobic oxidation of aldehydes to carboxylic acids in water by using an inorganic-ligand-supported copper catalyst was developed. This method was performed with the use of atmospheric oxygen as the sole oxidant under extremely mild aqueous conditions, and furthermore, a wide range of aldehydes with various functional groups were tolerated. The copper catalyst could be recycled and used in successive reactions at least six times without any appreciable degradation in performance. This method is operationally simple and avoids the use of high-costing, toxic, air/moisture-sensitive, and commercially unavailable organic ligands. The generality of this method gives it potential to be used on the industrial scale.
- Yu, Han,Ru, Shi,Zhai, Yongyan,Dai, Guoyong,Han, Sheng,Wei, Yongge
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p. 1253 - 1257
(2018/02/16)
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- Concise total synthesis of acylated phenolic glycosides vitexnegheteroin A and ovatoside D
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Starting from readily available vanillin and α-D-acetobromo glucose, two natural acylated phenolic glycosides vitexnegheteroin A and ovatoside D were synthesized for the first time in 4 steps with overall yields of 54% and 65%, respectively. The key steps involve the directly regioselective O-6 acylation of vanillin β-D-glucopyranoside with acyl chlorides, and simultaneous removal of the allyl protecting groups on the phenolic acid moiety and reduction of the aldehyde in the aglycon moiety by using Pd(PPh)3-NaBH4 system in one pot.
- Yan, Shiqiang,Ren, Sumei,Ding, Ning,Li, Yingxia
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- TETRAHYDRONAPHTHALENE AND TETRAHYDROISOQUINOLINE DERIVATIVES AS ESTROGEN RECEPTOR DEGRADERS
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The present disclosure relates to bifunctional compounds, which find utility as modulators of estrogen receptor (target protein). In particular, the present disclosure is directed to bifunctional compounds, which contain on one end at least one of a Von Hippel-Lindau ligand, a cereblon ligand, Inhibitors of Apoptosis Proteins ligand, mouse double-minute homolog 2 ligand, or a combination thereof, which binds to the respective E3 ubiquitin ligase, and on the other end a moiety which binds the target protein, such that the target protein is placed in proximity to the ubiquitin ligase to effect degradation (and inhibition) of target protein. The present disclosure exhibits a broad range of pharmacological activities associated with degradation/inhibition of target protein. Diseases or disorders that result from aggregation or accumulation of the target protein are treated or prevented with compounds and compositions of the present disclosure.
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Paragraph 14780; 1481
(2018/06/15)
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- Synthesis of Albicidin Derivatives: Assessing the Role of N-terminal Acylation on the Antibacterial Activity
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The peptide antibiotic albicidin, which is synthesized by the plant pathogenic bacterium, Xanthomonas albilineans, represents the most prominent member of a new class of antibacterial gyrase inhibitors. It shows remarkable antibacterial activities against Gram-positive and Gram-negative microorganisms. Its unique structure potentially represents a new lead structure for the development of an antibacterial drug. Here we report the synthesis of 14 albicidin derivatives with structural variations at the N-terminus, primarily investigating the effects of variation of cinnamoyl, phenylpropanoyl, and benzoyl residues. Gyrase inhibition in vitro and determination of minimal inhibitory concentrations were assessed in parallel. Activities in a nanomolar range and the importance of N-acylation were demonstrated.
- Kerwat, Dennis,Gr?tz, Stefan,Kretz, Julian,Seidel, Maria,Kunert, Maria,Weston, John B.,Süssmuth, Roderich D.
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p. 1899 - 1903
(2016/10/12)
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- Catalytic Fehling's Reaction: An Efficient Aerobic Oxidation of Aldehyde Catalyzed by Copper in Water
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The first example of homogeneous copper-catalyzed aerobic oxidation of aldehydes is reported. This method utilizes atmospheric oxygen as the sole oxidant, proceeds under extremely mild aqueous conditions, and covers a wide range of various functionalized aldehydes. Chromatography is generally not necessary for product purification.
- Liu, Mingxin,Li, Chao-Jun
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supporting information
p. 10806 - 10810
(2016/09/03)
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- The effect of photoisomerization on the enzymatic hydrolysis of polymeric micelles bearing photo-responsive azobenzene groups at their cores
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The design of stable polymeric micelles that can respond to specific stimuli is crucial for the development of smart micellar nanocarriers that can release their active cargo selectively at the target site, thus diminishing the therapeutic limitations due to non-selective damage to healthy tissues. Here we report the design and synthesis of photo- and enzyme-responsive amphiphilic PEG-dendron hybrids bearing one, two or four enzymatically cleavable azobenzene end-groups. These dual-responsive hybrids can respond to light through the reversible isomerization of the azobenzene end-groups from the non-polar trans isomer to the highly polar cis isomer and vice versa, upon UV and visible irradiation, respectively. The high structural precision of these hybrids, which emerges from the dendritic architecture, enabled a detailed study of the photoisomerization of the azobenzene end-groups with high molecular resolution. Remarkably, although the transition from trans-to-cis led to a significant increase in the polarity of the micellar cores, the micelles remained stable. Our kinetic studies show that although the trans isomer is a better substrate for the activating enzyme, the UV induced formation of the cis azobenzene end-groups led to significant acceleration of the enzymatic hydrolysis of the end-groups. These results provide strong indication that the enzyme cannot reach the core of the micelles and instead the end-groups have to leave the hydrophobic core in order to be exposed on the micelle's surface or even leave the micelle in order to allow their cleavage by the activating enzymes.
- Harnoy, Assaf J.,Slor, Gadi,Tirosh, Einat,Amir, Roey J.
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supporting information
p. 5813 - 5819
(2016/07/06)
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- Synthesis and characterization of liquid crystalline organosiloxanes containing 4-methoxyphenyl 4-(2-alkenyloxy)benzoate
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A series of new organosiloxane liquid crystalline materials based on the 4-methoxyphenyl-4-(ù-alkenyloxy)benzoate as mesogenic units have been synthesized and their mesomorphic and physical properties have been characterized. A series of new disiloxanes and trisiloxanes contain 4-methoxyphenyl 4-(ù-alkenyloxy)benzoate as mesogenic these were synthesized by addition of 4-methoxyphenyl 4-(ù-alkenyloxy)benzoate moiety to pentamethylhydrodisiloxane or heptamethylhydrotrisiloxane catalyzed by platinum divinyltetramethyldisiloxane complex. The thermal properties of this new series of thermotropic liquid-crystalline siloxanes were studied by differential scanning calorimetry and polarized optical microscope. Disiloxane series compounds were not showed any liquid crystal phase. Trisiloxanes series compounds exhibited nematic liquid crystal phase. The siloxane molecule helped to reduce the melting temperature. The thermal properties of the new siloxane series exhibited a pronounced odd-even effect with the length of alkyl segment.
- Chen, Cheng-Chih,Lin, Chih-Hung
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p. 1270 - 1274
(2016/04/10)
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- Influence of shorter backbone and cholesteric monomer percentage on the phase structures and thermal-optical properties of linear siloxane tetramers containing cholesterol and benzene methyl ether groups
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A series of new linear polysiloxane tetramers containing cholesterol and benzene methyl ether groups as side chains was successfully synthesized via a typical hydrosilylation reaction. Their chemical structures were confirmed by 1H-NMR, FT-IR and thermogravimetric analysis (TGA). A combination of analysis methods such as differential scanning calorimetry (DSC), polarized optical microscopy (POM), and X-ray diffraction was carried out to systematically investigate their phase transition behaviours and phase structures. The results revealed that the mesophase structures of all the polymers were greatly dependent on the molar content of the chiral cholesteric unit (Xchol). Polymers with Xchol below 0.60 or over 0.70 could develop a stable cholesteric phase or smectic A phase, while both smectic A and cholesteric phases could be formed for polymers with Xchol between 0.60 and 0.70. Besides, polymers with Xchol below 0.60, which developed a cholesteric phase with sufficiently wide temperature ranges in the entire mesomorphic state (minimum over 50 °C and maximum over 130 °C), could also exhibit tunable selective reflection wavelengths between 470-560 nm upon heating and arbitrarily regulated glass transition temperatures between 0-40 °C. As a result, a thermochromism liquid crystalline material for temperature sensors was successfully obtained. Surprisingly, different from the results previously reported, an unusual phenomenon of the centre selective light reflection wavelength (λm) vs. Xchol, which decreased dramatically (blue shift) at first, then had a remarkable red shift with increasing Xchol, was first observed.
- Yao, Wenhuan,Gao, Yanzi,Li, Fasheng,Zhang, Lanying,Yang, Zhou,Yang, Huai
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p. 87502 - 87512
(2016/09/23)
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- Construction of topological macromolecular side chains packing model: Study unique relationship and differences in LC-microstructures and properties of two analogous architectures with well-designed side attachment density
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A new series of linear-comb and 4-arm star-comb side chain liquid crystalline polymers (Lc-/Sc-SCLCPs) have been synthesized and characterized. The treatment of hydride siloxane-containing terminated liquid crystalline and high 1,2-/1,4- (high vinyl, hv/low vinyl, lv) linear or 4-arm star polybutadienes (L-/S-PBs) was conducted via the methods in combination of living anionic polymerization and "reverse" hydrosilylation to obtain SCLCPs with wide mesomorphic temperature range (ΔT) and narrow polydispersity index (PDI). The possible molecular arrangement model of two analogous hv-/lv-architectures was constructed, that was used to systematically investigate the effects of Lc- and Sc- topological morphology on liquid crystalline (LC) properties and molecular microstructures. SCLCPs exhibited the same smectic A phase around room temperature, but thermal properties were significantly different due to differences of interaction force resulting from different macromolecular side chains packing. Surprisingly, the trend of lv-SCLCP displaying the effects of topology on phase transitions and microstructures was just contrary to that of hv-topology. hv-Sc-SCLCPs containing high density mesogenic composition were desired to generate wider ΔT and higher molecular layer order in comparison with Lc analogues, which provided a unexpected analyzed model that are of interest to be explored. In particular, the uniaue differences of macromolecular aggregation state arrangement in liquid crystal state dependent on free cooling between hv-Lc- and Sc-SCLCPs were observed from POM.
- Han, Li,Ma, Hongwei,Li, Yang,Wu, Jian,Xu, Hanyan,Wang, Yurong
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p. 925 - 941
(2015/06/15)
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- Discovery of benzamide analogs as negative allosteric modulators of human neuronal nicotinic receptors: Pharmacophore modeling and structure-activity relationship studies
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The present study describes our ongoing efforts toward the discovery of drugs that selectively target nAChR subtypes. We exploited knowledge on nAChR ligands and their binding site that were previously identified by our laboratory through virtual screenings and identified benzamide analogs as a novel chemical class of neuronal nicotinic receptor (nAChR) ligands. The lead molecule, compound 1 (4-(allyloxy)-N-(6-methylpyridin-2-yl)benzamide) inhibits nAChR activity with an IC50 value of 6.0 (3.4-10.6) μM on human α4β2 nAChRs with a ~5-fold preference against human α3β4 nAChRs. Twenty-six analogs of compound 1 were also either synthesized or purchased for structure-activity relationship (SAR) studies and provided information relating the chemical/structural properties of the molecules to their ability to inhibit nAChR activity. The discovery of subtype-selective ligands of nAChRs described here should contribute significantly to our understanding of the involvement of specific nAChR subtypes in normal and pathophysiological states.
- Yi, Bitna,Long, Sihui,González-Cestari, Tatiana F.,Henderson, Brandon J.,Pavlovicz, Ryan E.,Werbovetz, Karl,Li, Chenglong,McKay, Dennis B.
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p. 4730 - 4743
(2013/07/26)
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- The synthesis of selected phase II metabolites - O-glucuronides and sulfates of drug development candidates
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We have summarized methods for the preparation of phase II metabolites which have proven to be successful in our laboratory for the synthesis of selected O-glucuronides and sulfates of recent drug development candidates. The syntheses of the O-glucuronides AVE0897 O-acylglucuronide 7, AVE2268 O-glucuronide 12, SAR7226 O-glucuronide 21 and the preparation of the sulfates 28 of AVE2268 and MDL107292 33 are described in detail. Analytical aspects related to phase II metabolites and specific chromatographic methods of very polar compounds are discussed. ARKAT-USA, Inc.
- Atzrodt, Jens,Derdau, Volker,Holla, Wolfgang,Sandvoss, Martin
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p. 257 - 278
(2013/09/24)
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- Synthesis of a Heparan Sulfate Mimetic Library Targeting FGF and VEGF via Click Chemistry on a Monosaccharide Template
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A disulfated methyl 6-azido-6-deoxy-α-D-mannopyranoside template was used as a core structure for binding to the angiogenic growth factors FGF-1, FGF-2, and VEGF. The core structure was diversified in a rapid, parallel manner by employing the CuI-catalyzed Huisgen azide-alkyne cycloaddition ("click") reaction. The diversity was further extended by incorporating a Swern oxidation-Wittig reaction sequence on a click adduct of propargyl alcohol. Thus, the sulfated core was linked by various spacers to selected hydrophobic or polar motifs, which were designed to probe the protein surface surrounding the cationic heparan sulfate binding sites of the growth factors in order to improve affinity and selectivity. The affinities of the compounds for the growth factors were measured by surface plasmon resonance solution affinity assays. A lead compound was identified with micromolar binding affinity toward both FGF-1 and VEGF (Kd=84 and 49μM, respectively) and good selectivity over FGF-2 (29- and 51-fold, respectively).
- Liu, Ligong,Li, Caiping,Cochran, Siska,Jimmink, Shane,Ferro, Vito
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scheme or table
p. 1267 - 1275
(2012/08/08)
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- Chiral nematic liquid crystalline copolymers as stationary phase materials in capillary gas chromatography
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A new series of liquid crystalline polysiloxanes with a very wide range of mesomorphic temperatures has been prepared. They contain 4-cholesteryl-(10- undecen-1-yloxy) biphenyl-4'-carboxylate mesogenic and 4-biphenyl-4'- allyloxybenzoate mesogenic side groups displaying enantiotropic nematic and chiral nematic phases. The mesomorphic polysiloxane specimen with the widest temperature range was used as the stationary phase in a gas chromatography capillary column and it showed unique separation properties for polycyclic aromatic compounds.
- Lee, Yi-Wen,Lin, Chih-Hung
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scheme or table
p. 5190 - 5194
(2012/09/21)
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- New thiadiazole derivatives
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The present invention relates to thiadiazole derivatives of formula (I), to processes for their preparation and to pharmaceutical compositions containing them. These compounds are potent agonists of S1P1 receptors and thus, they are useful in the treatment, prevention or suppression of diseases and disorders known to be susceptible to improvement by sphingosine-1-phosphate receptors agonists (S1P1), such as autoimmune diseases, chronic immune and inflammatory diseases, transplant rejection, malignant neoplastic diseases, angiogenic-related disorders, pain, neurological diseases, viral and infectious diseases.
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Page/Page column 39
(2011/04/25)
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- NEW THIADIAZOLE DERIVATIVES
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The present invention relates to thiadiazole derivatives of formula (I), to processes for their preparation and to pharmaceutical compositions containing them. These compounds are potent agonists of S1P1 receptors and thus, they are useful In the treatment, prevention or suppression of diseases and disorders known to be susceptible to improvement by sphingosine-1-phosphate receptors agonists (S1P1), such as autoimmune diseases, chronic immune and inflammatory diseases, transplant rejection, malignant neoplastic diseases, angiogenic-related disorders, pain, neurological diseases, viral and infectious diseases.
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Page/Page column 59
(2011/04/24)
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- Synthesis of isotopically labelled SGLT inhibitors and their metabolites
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Isotopically labelled analogues of two structurally very similar SGLT inhibitors AVE2268 (1a) and AVE8887 (1b) have been synthesized by various routes. The radioactive labelled [14C]-AVE2268 was prepared in five steps including a Friedel-Crafts acylation as the key step for the 14C-label introduction. For [14C]-AVE8887 the same synthetic approach was not successful and therefore an alternative thiophene metallation/Weinreb amide sequence was developed. This pathway was also applied to obtain stable isotopically labelled analogues of both AVE2268 and AVE8887. Finally, the synthesis of two metabolites, sulfate 12 and glucuronide 13 were achieved by applying interesting protecting group and oxidation strategies.
- Derdau, Volker,Fey, Thorsten,Atzrodt, Jens
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experimental part
p. 1472 - 1482
(2010/04/02)
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- Mesophase structure of low-wetting liquid crystalline polyacrylates with new perfluoroalkyl benzoate side groups
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The synthesis, thermal behavior, bulk microstructure, and wettability of new polyacrylates carrying spaced 4-perfluorohexylpropyl benzoate and 4-perfluorooctylpropyl benzoate units in the side groups were Investigated. X-ray diffraction analysis proved the formation of different smectic mesophases (SmI2, SmF2, and SmC2) and the evolution of their structures and lattice parameters with temperature. The mesophase polymorphic behavior depended on the length of the perfluorinated chain segment in the repeat unit. The electron density profiles along the smectic layer normal were drawn and provided a deeper insight into the packing of the side chains in a tilted, double layer structure. Thin polymer films were cast from solution, and their low wettability was established by measurements of contact angles with different probing liquids. We suggest that the hydrophobicity and lipophobicity of the films are enhanced by the mesophase surface structure which is mediated by the high-order, mesophase bulk structure.
- Martinelli, Elisa,Paoli, Francesca,Gallot, Bernard,Galli, Giancarlo
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experimental part
p. 4128 - 4139
(2011/10/30)
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- New liquid-crystalline elastomers: 1. Synthesis, structure, and phase behavior of a series of mesogenic crosslinking agents containing reactive bifunctional groups
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The synthesis of eight mesogenic crosslinking agents (1c-8c) containing reactive bifunctional groups is described. The chemical structures were characterized by Fourier transform infrared (FTIR) and 1H nuclear magnetic resonance (NMR) spectra. The mesomorphism was investigated by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). The compounds 1c, 2c, 3c, 5c, 6c, and 8c showed an enantiotropic nematic phase. In addition, 5c exhibited a smectic A (SmA) phase on cooling; 4c exhibited a smectic C (SmC) phase, a SmA phase, and a nematic phase and a monotropic a smectic B (SmB) phase on cooling. 7c revealed an SmA phase and a nematic phase and a monotropic SmC phase on cooling. Copyright Taylor & Francis Group, LLC.
- Xu, Xiao-Xu,Hong, Zhe,Liu, Fei
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scheme or table
p. 52 - 62
(2011/09/15)
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- Concise strategy for the synthesis of elevenmembered and ansa-bridged thirteen-membered lactone macrolides by ring-closing metathesis reaction
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The eleven-membered macrolides and thirteen-membered ansa-bridged macrolides have been synthesized successfully ring-closing metathesis reaction in the absence of the additive Ti(OiPr)4, which is essential for the metathesis of the ester precursors.
- Majumdar, Krishna C.,Chattopadhyay, Buddhadeb,Ansary, Inul
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experimental part
p. 472 - 477
(2009/10/17)
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- SHAPE MEMORY MAIN-CHAIN SMECTIC-C ELASTOMERS
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Shape memory main-chain smectic-C elastomers are described, as are methods for their preparation and monomers used in such methods. The elastomers are prepared by hydrosilylation of a reaction mixture including a liquid crystalline diene, a crosslinking agent, and a bis(silyl hydride) compound. The elastomers exhibit shape-memory properties and spontaneously reversible shape changes. They are useful for fabrication of shape memory articles including, for example, implantable medical devices, contact lenses, reversible embossing media, and Fresnel lenses.
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Page/Page column 9
(2009/10/01)
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- Facile and selective deallylations of esters under 'aqueous' free-radical conditions
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The conversion of allyl esters into carboxylic acids using radical initiators has been achieved in high yields in aqueous media. Georg Thieme Verlag Stuttgart.
- Perchyonok, V. Tamara,Ryan, Sarah J.,Langford, Steven J.,Hearn, Milton T.,Tuck, Kellie L.
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body text
p. 1233 - 1235
(2009/04/05)
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- Synthesis of novel aromatic macrolactones via ring closing metathesis of substituted phenylalkanoic acid allylic esters
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(Chemical Equation Presented) Stable aromatic macrolactones have been synthesized and characterized from 2- and 3-substituted phenylalkanoic acid systems in modest yields.
- Brown, David P.,Duong, Hoan Q.
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p. 435 - 443
(2008/09/19)
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- ALLYLQXY AND ALKYLOXY BENZOIC ACID DELIVERY AGENTS
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The present invention relates to pharmaceutical compounds for delivering active agents, such as biologically or chemically active agents, to a target. The invention also relates to pharmaceutical compositions comprising at least one delivery agent compound of the present invention and at least one active agent, and unit dosage forms comprising such compositions. Methods for the preparation and administration of the pharmaceutical compositions are also disclosed.
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Page/Page column 32
(2008/12/07)
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- Aerobic oxidation of alcohol in aqueous solution catalyzed by gold
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The heterogeneous oxidation catalyzed by supported gold nanoparticles has been relatively well studied. In comparison, the oxidation of alcohols catalyzed by ligand-supported gold complexes was rarely reported. Herein a general method is demonstrated to oxidize secondary and primary benzyl and allylic alcohols to carbonyl compounds via Au(I) catalyzed reaction in air and water. Primary mechanistic studies indicated that the catalytic pathway is different from those catalyzed by solid-supported gold nanoparticles.
- Li, Huanrong,Guan, Bingtao,Wang, Wenjin,Xing, Dong,Fang, Zhao,Wan, Xiaobing,Yang, Liping,Shi, Zhangjie
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p. 8430 - 8434
(2008/02/08)
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- A simple method for chemoselective phenol alkylation
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A simple and effective method for chemoselective alkylation of phenol over carboxylic acid using a 40% aqueous solution of tetrabutylphosphonium hydroxide that affords the desired phenyl ethers in 82-99% yield is described.
- Liu, Pingli,Huang, Liang,Faul, Margaret M.
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p. 7380 - 7382
(2008/03/13)
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- Study on an electrorheological effect of side-chain polysiloxanes including fluorine atoms by the preshearing method
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Side-chain liquid-crystalline polysiloxane derivatives possessing fluorinated mesogens that have positive dielectric-anisotropy parallel to the long axis of mesogen were synthesized to study phase-transition behavior and electrorheological (ER) effect of the polymers with a preshearing method. About 2000Pa increments in shear stress could be obtained after preshearing as an ER effect. In addition, shear rate dependence on shear stress as a function of temperature was investigated. As a result, it was shown that the preshearing treatment with high shear rate was important to generate a larger ER effect.
- Kaneko, Kosuke,Miwa, Yusuke,Nakamura, Naotake
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- FIBROSIS INHIBITOR
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Medicament being useful as a fibrosis inhibitor for organs or tissues, which comprises a compound of the formula (I): wherein Ring Z is optionally substituted pyrrole ring, etc.; W2 is -CO-, -SO2-, optionally substituted C1-C4 alkylene, etc.; Ar2 is optionally substituted aryl, etc.; W1 and Ar1 mean the following (1) and (2):(1) W1 is optionally substituted C1-C4 alkylene, etc.; Ar1 is optionally substituted bicyclic heteroaryl having 1 to 4 nitrogen atoms as ring-forming atoms:(2) W1 is optionally substituted C2-C5 alkylene, optionally substituted C2-C5 alkenylene, etc.; and Ar1 is aryl or monocyclic heteroaryl, which is substituted by carboxyl, alkoxycarbonyl, etc. at the ortho- or meta-position thereof with respect to the binding position of W1, or a pharmaceutically acceptable salt thereof.
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- Potential antipsoriatic avarol derivatives as antioxidants and inhibitors of PGE2 generation and proliferation in the HaCaT cell line
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The synthesis and structure-activity relationships for a series of 14 new avarol derivatives as antioxidants and inhibitors of cell proliferation and PGE2 generation in human keratinocytes are described. Compound 6 (thiosalicylic derivative) was the most potent inhibitor of superoxide generation in human neutrophils and also potently inhibited PGE2 generation in the human keratinocyte HaCaT cell line. Compound 7 (3′-methylaminoavarone) presented the best antiproliferative profile, by the inhibition of 3H-thymidine incorporation in HaCaT cells, with potency similar to the reference compound anthralin. None of the avarol derivatives showed any sign of cytotoxicity measured as LDH release in treated keratinocytes. The potency and pharmacological profile of derivatives are also discussed.
- Amigo, Maria,Terencio, Maria Carmen,Mitova, Maya,Iodice, Carmine,Paya, Miguel,De Rosa, Salvatore
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p. 1459 - 1463
(2007/10/03)
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- Facile and selective deallylation of allyl ethers using diphosphinidenecyclobutene-coordinated palladium catalysts
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(π-Allyl)palladium triflate bearing a 1,2-bis(4-methoxyphenyl)-3,4- bis(2,4,6-tri-tert-butylphenylphosphinidene)cyclobutene ligand (DPCB-OMe), [Pd(η3-C3H5)(DPCB-OMe)]OTf, efficiently catalyzes deallylation of a variety of allyl ethers in aniline to give corresponding alcohols in high yields under mild conditions. The reactions can be performed in air without loss of a variety of functionalities including vinyl, alkynyl, hydroxy, acetoxy, silyloxy, and acetal groups. Allyl 2-allyloxybenzoate selectively undergoes deallylation of the allyloxy group to give allyl salicylate in quantitative yield.
- Murakami, Hiromi,Minami, Tatsuya,Ozawa, Fumiyuki
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p. 4482 - 4486
(2007/10/03)
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- Pyrrole derivatives
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Pyrrole derivatives represented by the following formula: wherein Ring Z is an optionally substituted pyrrole ring, etc.; W2 is —CO—, —SO2—, an optionally substituted C1-C4 alkylene, etc.; Ar2 is an optionally substituted aryl, etc.; W2 and Ar1 mean the following (1) and (2): (1) W1 is an optionally substituted C1-C4 alkylene, etc.; Ar1 is an optionally substituted bicyclic heteroaryl having 1 to 4 nitrogen atoms as ring-forming atoms: (2) W1 is an optionally substituted C2-C5 alkylene, an optionally substituted C2-C5 alkenylene, etc.; and Ar1 is an aryl or monocyclic heteroaryl, which are substituted by carboxyl, an alkoxycarbonyl, etc. at the ortho- or meta-position thereof with respect to the binding position of W1, or a pharmaceutically acceptable salt thereof These compounds are useful as medicaments such as a fibrosis inhibitor for organs or tissues.
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- Estrogen receptor modulators: Identification and structure-activity relationships of potent ERα-selective tetrahydroisoquinoline ligands
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As part of a program aimed at the development of selective estrogen receptor modulators (SERMs), tetrahydroisoquinoline derivative 27 was discovered by high throughput screening. Successive replacements of the p-F substituent of 27 by an aminoethoxy side chain and of the 1-H of the tetrahydroisoquinoline core by a 1-Me group provided analogues 19 and 20. These compounds showed potencies in a cell-based reporter gene assay (ERE assay) varying between 0.6 and 20 nM and displayed antagonist behaviors in the MCF-7 human breast adenocarcinoma cell line with IC50s in the range of 2-36 nM. The effect of N-phenyl substituents on the activity and pharmacokinetic properties of tetrahydroisoquinoline analogues was explored. As a result of this investigation, two potent derivatives bearing a p-F N-aryl group, 19c and 20c, were discovered as candidates suitable for further profiling. To gain insight into the ligand-receptor interaction, the X-ray crystallographic structure of the 1-H tetrahydroisoquinoline derivative (R)-18a in complex with ERα-ligand binding domain (LBD)301-553/C→S triple mutant was solved to 2.28 A?. An overlay of this X-ray crystal structure with that reported for the complex of ERαLBD301-553/carboxymethylated C and raloxifene (5) shows that both compounds bind to the same cleft of the receptor and display comparable binding modes, with differences being observed in the conformation of their "D-ring" phenyl groups.
- Renaud, Johanne,Bischoff, Serge Fran?ois,Buhl, Thomas,Floersheim, Philipp,Fournier, Brigitte,Halleux, Christine,Kallen, Joerg,Keller, Hansjoerg,Schlaeppi, Jean-Marc,Stark, Wilhelm
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p. 2945 - 2957
(2007/10/03)
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- Side-Chain Cholesteric Liquid Crystalline Elastomers Derived from a Mesogenic Cross-Linking Agent
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The synthesis of the two monomers M1 and M2 and a series of new side-chain cholesteric liquid crystalline elastomers P 2-P8 is presented. The chemical structures of the monomers and elastomers obtained were confirmed by FTIR or 1H NMR spectroscopy. The cross-link density of the elastomers was determined by swelling experiments. The mesomorphic properties were investigated by differential scanning calorimetry (DSC), thermogravimetric analyses (TGA), polarizing optical microscopy (POM), and X-ray diffraction (XRD) measurements. Monomer M1 showed a cholesteric phase, and M2 revealed smectic and nematic phases. The effect of the cross-link density on the phase behavior of P2-P8 is discussed. Elastomers P 2-P6 containing less than 12 mol % of the cross-linking units displayed elasticity, reversible liquid crystalline phase transition, wide mesophase temperature ranges, and high thermal stability. Elastomer P 7 displayed stress-induced birefringence, and P8 showed only elasticity with no other texture. Experimental results demonstrated that the glass transition temperatures increased, and the isotropization temperatures and the mesophase temperature ranges of P2-P 6 decreased with increasing cross-link density.
- Hu, Jian-She,Zhang, Bao-Yan,Jia, Ying-Gang,Chen, Song
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p. 9060 - 9066
(2007/10/03)
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- A simple, mild and efficient procedure for selective cleavage of prenyl esters using silica-supported sodium hydrogen sulphate as a heterogenous catalyst
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Prenyl esters were selectively and efficiently cleaved under slightly acidic reaction conditions using silica-supported sodium hydrogen sulfate as a heterogenous catalyst at room temperature to regenerate the parent carboxylic acids in very high yields.
- Ramesh,Mahender,Ravindranath,Das, Biswanath
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p. 1465 - 1467
(2007/10/03)
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- Induction of smectic layering in nematic liquid crystals using immiscible components. 5. Laterally attached side-chain liquid crystalline poly(norbornene)s and their low molar mass model compounds with short fluorocarbon segments
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5-[[[2′,5′-Bis[(4″-n-((perfluoroalkyl)alkoxy)benzoyl)oxy] benzyl]oxy]carbonyl]bicyclo[2.2.1]hept-2-enes with short fluorocarbon segments were polymerized by ring-opening metathesis polymerization in THF at room temperature using Mo(CHCMe2Ph)(N-2,6-iPr2Ph)(OtBu) 2 as the initiator. Although hydrocarbon and fluorocarbon segments as short as three methylenic units each induce smectic layering in the corresponding 2,5-bis{[4′-(n-(perfluoroalkyl)alkoxy)benzoyl]oxy}toluene model compounds, the polymers require at least eight and three, or five and four methylenic units in the hydcrocarbon and fluorocarbon segments, respectively, to organize into smectic layers; polymers with shorter hydrocarbon and/or fluorocarbon segments are nematic.
- Small, Aaron C.,Pugh, Coleen
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p. 2105 - 2115
(2007/10/03)
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