15949-84-5Relevant articles and documents
Optically induced linking of protein and nanoparticles to gold surfaces
Moth-Poulsen, Kasper,Kofod-Hansen, Vesna,Kamounah, Fadhil S.,Hatzakis, Nikos S.,Stamou, Dimitrios,Schaumburg, Kjeld,Christensen, J?rn B.
, p. 1056 - 1061 (2010)
Attachment of molecules and proteins to surfaces is of great interest for the development of a large variety of applications. We present herein a novel approach to efficiently couple a molecule of choice to biological building blocks. We synthesized and employed a new derivative of 5-bromo-7-nitroindoline to attach nucleophilic molecules and proteins to gold surfaces by photochemical activation. The reaction can be seen as a photoactivated alternative to the activated ester type chemistries that are commonly used to attach proteins or molecules to surfaces. We characterize the reaction by UV-vis and NMR spectroscopy, and as test of principle experiment, we show that we can attach proteins to surfaces and demonstrate that we can functionalize gold nanoparticles by this optically induced cross-linking reaction.
Fabrication of Gradient and Patterned Organic Thin Films by Bipolar Electrolytic Micelle Disruption Using Redox-Active Surfactants
Zhou, Yaqian,Shida, Naoki,Tomita, Ikuyoshi,Inagi, Shinsuke
, p. 14620 - 14629 (2021)
Bipolar electrochemistry could be regarded as a powerful approach for selective surface modification due to the beneficial feature that a wirelessly controllable potential distribution on bipolar electrodes (BPEs). Herein we report a bipolar electrolytic micelle disruption (BEMD) system for the preparation of shaped organic films. A U-shaped bipolar electrolytic system with a sigmoidal potential gradient on the BPE gave gradient-thin films including various interesting organic compounds, such as a polymerizable monomer, an organic pigment and aggregation induced emission (AIE) molecules. The gradient feature was characterized by UV–Vis absorption, thickness measurements and surface morphology analysis. Corresponding patterned films were also fabricated using a cylindrical bipolar electrolytic setup that enables site-selective application of the potential on the BPE. Such a facile BEMD approach will open a long-term perspective with respect to organic film preparation.
Electrochromism of a bipolar reversible redox-active ferrocene-viologen linked ionic liquid
Tahara, Hironobu,Baba, Rei,Iwanaga, Kodai,Sagara, Takamasa,Murakami, Hiroto
, p. 2455 - 2458 (2017)
A ferrocene-viologen linked “bipolar” type redox-active ionic liquid ([FcC11VC1][TFSI]2) was synthesized as an electrochromic (EC) material that functions without any other additives: solvents, supporting electrolytes and sacrificial agents. The efficiency of a prototype symmetrical EC cell was 70 cm2 C?1 at 1.0 V. The EC process was stable even after over 10?000 potential cycles.
Supramolecular assemblies formed by new L-lysine derivatives of viologens?
Suzuki,Waraksa,Nakayama,Hanabusa,Kimura,Shirai
, p. 2012 - 2013 (2001)
L-Lysine derivatives of viologens form supramolecular assemblies of fibers and ribbons in some aromatic solvents, and the charge separation reaction in these self-assembling systems proceeds with a similar efficiency to the MV2+ system.
DNA-binding and photocleavage properties of cationic porphyrin-anthraquinone hybrids with different lengths of links
Zhao, Ping,Xu, Lian-Cai,Huang, Jin-Wang,Fu, Bo,Yu, Han-Cheng,Zhang, Wei-Hong,Chen, Jian,Yao, Jun-Hua,Ji, Liang-Nian
, p. 278 - 287 (2008)
Four cationic porphyrin-anthraquinone (Por-AQ) hybrids differing in lengths of flexible alkyl linkage, 5-[4-(1-N-anthraquinonon-yl)-l-oxophenyl]-10,15,20-tris(N-methylpyridinium-4-yl)porphyrin triiodide, (l = acetyl, pentanoyl, octanoyl, undecanoyl, designed as [AQATMPyP]I3, [AQPTMPyP]I3, [AQOTMPyP]I3 and [AQUTMPyP]I3, respectively, see Fig. 1), were synthesized and their interactions with DNA were investigated. The results of spectroscopic, denaturation and viscosity measurements suggest that [AQATMPyP]I3 binds to DNA through non-intercalative mode while the other three hybrids with longer links bind via bis-intercalative mode. Ethidium bromide (EB) competition experiment was carried out to determine the binding constants (Kb) of these compounds for CT DNA, and [AQPTMPyP]I3 shows the largest Kb among these hybrids. The photocleavage mechanism and wavelength-dependent cleaving abilities of these hybrids to pBR322 plasmid DNA were also comparably investigated.
Supercapacitors based on polyelectrolyte/ferrocenyl-surfactant complexes with high rate capability
Tan, Guiping,Cheng, Zhiyu,Qiu, Yongfu,Huang, Weiqing,Fan, Hongbo,Ren, Biye
, p. 31632 - 31638 (2016)
In this paper, a composite of the Polyelectrolyte/Ferrocenyl-Surfactant Complexes (PFSC) coated on carbon paper (CP) was applied as an electrode material for supercapacitors. The as-prepared composite possessed a specific capacitance as high as 214 F g-1 calculated from discharge curve with a current density of 0.8 A g-1 and this observation was deemed to be because of its ferrocenyl moieties. Furthermore, the specific capacitances calculated from cyclic voltammograms were 145 and 103 F g-1 at the potential scan rates of 20 and 50 mV s-1, which kept at 77.6% and 55.4% of the corresponding value at 10 mV s-1 (187 F g-1). This suggested that the composite possessed a good rate capability as a novel redox active electrode material for pseudo-capacitors. In short, for the first time the composite PFSC/CP was reported as a promising electrode material for efficient supercapacitors.
Array-based detection of persistent organic pollutants via cyclodextrin promoted energy transfer
Serio, Nicole,Moyano, Daniel F.,Rotello, Vincent M.,Levine, Mindy
, p. 11615 - 11618 (2015)
We report herein the selective array-based detection of 30 persistent organic pollutants via cyclodextrin-promoted energy transfer. The use of three fluorophores enabled the development of an array that classified 30 analytes with 100% accuracy and identified unknown analytes with 96% accuracy, as well as identifying 92% of analytes in urine.
Comprehensive investigation of self-assembled monolayer formation on ferromagnetic thin film surfaces
Hoertz, Paul G.,Niskala, Jeremy R.,Dai, Peng,Black, Hayden T.,You, Wei
, p. 9763 - 9772 (2008)
We report a simple, universal method for forming high surface coverage SAMs on ferromagnetic thin (≤100 nm) films of Ni, Co, and Fe. Unlike previous reports, our technique is broadly applicable to different types of SAMs and surface types. Our data constitutes the first comprehensive examination of SAM formation on three different ferromagnetic surface types using two different surface-binding chemistries (thiol and isocyanide) under three different preparation conditions: (1) SAM formation on electroreduced films using a newly developed electroreduction approach, (2) SAM formation on freshly evaporated surfaces in the glovebox, and (3) SAM formation on films exposed to atmospheric conditions beforehand. The extent of SAM formation for all three conditions was probed by cyclic voltammetry for surfaces functionalized with either (11-thiolundecyl)ferrocene (Fc-(CH2)11-SH) or (11-isocyanoundecyl)ferrocene (Fc-(CH2)11-NC). SAM formation was also probed for straight-chain molecules, hexadecanethiol and hexadecaneisocyanide, with contact angle measurements, X-ray photoelectron spectroscopy, and reflection-absorption infrared spectroscopy (RAIRS). The results show that high surface coverage SAMs with low surface-oxide content can be achieved for thin, evaporated Ni and Co films using our electroreduction process with thiols. The extent of SAM formation on electroreduced films is comparable to what has been observed for SAMs/Au and to what we observe for SAMs/Ni, Co, and Fe samples prepared in the glovebox.
Synthesis of [14,14,14-2H3] 12-hydroxytetradecanoic acid and [13,14-2H2] 11-hydroxytetradecanoic acid useful as tracers to study a (11E)-desaturation reaction in Spodoptera littoralis
Navarro,Fabrias,Camps
, p. 439 - 443 (1996)
The synthesis of deuterium labeled 11- and 12-hydroxytetradecanoic acids to study a (11E) desaturase in the moth Spodoptera littoralis is reported. [14,14,14-2H3] 12-hydroxytetradecanoic acid was synthesized in four steps from 11-iodo-1-undecene in 49% overall yield. Deuterium was introduced by reaction of an epoxy ester with (CD3)2CuLi. The preparation of [13,14-2H2] 11-hydroxytetradecanoic acid was carried out in six steps from 11-bromoundecanoic acid in 55% overall yield. In this case, label was introduced by deuteration of an homoallyl alcohol with D2, using the Wilkinson catalyst. Incubation of pheromone glands with either of both acids did not lead to the formation of the labeled (11E)-tetradecanoic acid.
Molecular Conformation in Charge Tunneling across Large-Area Junctions
Chen, Jiahao,Du, Chuanshen,Norris, Sean R.,Thakur, Abhishek,Thuo, Martin,Vanveller, Brett
, p. 13878 - 13886 (2021)
Self-assembled monolayers are predicated on thermodynamic equilibrium; hence, their properties project accessible relaxation pathways. Herein, we demonstrate that charge tunneling correlates with conformational degrees of freedom(s). Results from open chain and cyclic head groups show that, as expected, distribution in tunneling data correlates with the orientation of the head group, akin to the odd-even effect and more importantly the degree of conformational freedom, but fluctuates with applied bias. Trends in nature of distributions in current density illuminate the need for higher statistical moments in understanding these rather dynamic systems. We employ skewness, kurtosis, and estimation plots to show that the conformational degree of freedom in the head group significantly amplifies the odd-even effect and may lead to enhanced or perturbed tunneling based on whether the head group is on an odd- or even-parity spacer.
Synthesis and properties of polythiophene containing mesogenic group at 3-position of thiophene ring
Koide,Iida
, p. 427 - 436 (1995)
Various kinds of polythiophene derivatives were synthesized and thermal properties were examined by DSC, polarized microscopic and X-ray diffraction observations. Fusibility and solubility of these polymers deeply depends upon the polymerization methods and polarity of the mesogenic group. Polymerization was carried out by oxidation and poly-condensation methods. The polarity at the end of mesogenic group plays an important role for solubility and fusibility of the polymer in the case of oxidative polymerization. 3-Substituted polythiophene having polar group such as cyano or nitro at the end of mesogenic group was soluble in polar solvent and fusibility at higher temperature. The polymer having polar group at the end of mesogenic group prepared by mild polymerization condition such as polycondensation exhibited a clear smectic texture and also showed electrochemically active by cyclic voltammograms.
The photoinduced electron transference of porphyrin-anthraquinone dyads bridged with different lengths of links
Zhao, Ping,Huang, Jin-Wang,Xu, Lian-Cai,Ma, Li,Ji, Liang-Nian
, p. 437 - 442 (2011)
The photoinduced electron transference (PET) interaction in porphyrin containing donor-acceptor (D-A) molecules is of great importance in nature and a significant part of the PET research has been devoted to the study of its mechanism ("through-space" or "through-bond") in these decades. Herein we synthesized a series of covalently linked porphyrin-anthraquinone dyads (Por-Cn-AQ) bridged with flexible alkoxy chains at different lengths (n = 1, 4, 10) and investigated their intramolecular PET using a combination of electronic absorption, steady-state fluorescence and decayed luminescence spectra. The experimental results show that the PET efficiency depends on the length of the flexible linkage between the porphyrin and anthraquinone moieties. Meanwhile, theoretical calculation applying the density functional theory (DFT) was also carried out to give the frontier orbital distribution and the optimized structures of these dyads. It is found that the orientation of the dyad with high PET efficiency is disadvantageous to π-π interaction. Thus, the PET of these dyads seemingly is best compatible with a "through-bond" (superexchange) mechanism.
Selective reductive desorption of a SAM-coated gold electrode revealed using fluorescence microscopy
Shepherd, Jeff L.,Kell, Arnold,Chung, Emily,Sinclar, Chad W.,Workentin, Mark S.,Bizzotto, Dan
, p. 8329 - 8335 (2004)
The reductive desorption of a self-assembled monolayer (SAM) of a fluorescent thiol molecule (BodipyC10SH) from Au was characterized using electrochemistry and epi-fluorescence microscopy. Molecular luminescence is quenched near a metal surface, so fluorescence was only observed for molecules reductively desorbed and then separated from the electrode surface. Fluorescence imaging showed that reductive desorption was selective, with desorption occurring from different regions of the Au electrode depending on the extent of the negative potential excursion. When desorbed, the molecules were sufficiently mobile, diffusing away from the electrode surface, thereby preventing oxidative readsorption. At sufficiently negative desorption potentials, all of the thiol was desorbed from the electrode surface, resulting in fluorescence at the air/solution interface. The selective removal of the thiol monolayer from distinct regions was correlated to features on the electrode surface and was explained through potential-dependent interfacial energies. This in situ electrofluorescence microscopy technique may be useful in sensor development.
A Novel Synthesis of 1,21-Heneicosanedioic Acid
Tsai, K. R.,Newman, Melvin S.
, p. 4785 - 4786 (1980)
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Redox-controlled reversible micelles transition and lyotropic liquid-crystalline behavior of novel polymerizable ferrocenyl surfactants
Cheng, Zhiyu,Chang, Xueyi,Qiu, Yongfu,Tan, Guiping,Cheng, Faliang,Fan, Hongbo,Ren, Biye
, p. 81 - 87 (2018)
A novel photopolymerizable surfactant with ferrocenyl group, (11-ferrocenylundecyl) (ethyl methacrylate) dimethylammonium bromide (I+), was synthesized through the reaction of 11-bromoundecyl ferrocene and N,N-(dimethylamino) ethyl methacrylate. Based on the results of voltammetric cycle, the small potential difference ΔE was 72 mV, which indicates that the I+ has good redox reversibility. The critical micellar concentration (CMC) values were about 0.5 and 22.7 mM for I+ in the reduction (CMCred) and oxidation state (CMCox) and it could aggregate and disaggregate by using redox reaction and photopolymerization when its concentrations was between their CMCred and CMCox values. The lyotropic liquid-crystalline properties of I+ in water were investigated by X-ray diffraction (XRD) and plarized optical microscope (POM). The results indicate when the concentration of the I+ solution over 40 wt %, an ordered lamellar liquid crystal structure was formed. With increasing concentration, the nanoscopic long-range order improved. Moreover, the lyotropic liquid-crystalline properties of I+ could also be controlled by using redox reaction and photopolymerization. In a word, the novel polymerizable ferrocenyl surfactants are good environmental responsive materials and can potentially act as the drug carrier and the scavenger for removing dissolved organic impurities in water.
Separately enhanced dual emissions of the amphiphilic derivative of 2-(2′-hydroxylphenyl) benzothiazole by supramolecular complexation
Wu, Chengfeng,Jin, Yingzhi,Li, Dahua,Ding, Lan,Xing, Yuzhi,Zhang, Kaicheng,Song, Bo
, p. 4374 - 4379 (2018)
Here, we report separately enhanced dual emissions of the amphiphilic derivative of 2-(2′-hydroxyphenyl)benzothiazole (denoted as HBT-11) by supramolecular complexation with cyclodextrins (CDs). When dispersed in water, HBT-11 shows two relatively weak emission bands, which can be assigned to the emissions of enol- and keto-forms, the two tautomers, owing to excited-state intramolecular proton transfers. Upon the addition of α-CD and β-CD, the keto- and enol-emissions, respectively, are separately enhanced; the enhancement effect is due to the formation of HBT-11/α-CD and HBT-11/β-CD complexes through multiple hydrogen bonding and host-guest interactions, respectively. It is worth to note that the keto-emission caused by the complex of HBT-11/α-CD has a much shorter wavelength compared with that of the aggregates formed by pure HBT-11. To the best of our knowledge, this is the first time that a study on keto-emission of the isolated HBT chromophore has been reported.
Synthesis of Long-Chain Alkanoyl Benzenes by an Aluminum(III) Chloride-Catalyzed Destannylative Acylation Reaction
Roemer, Max,Keaveney, Sinead T.,Proschogo, Nicholas
, p. 9007 - 9022 (2021/07/20)
This paper describes the facile synthesis of haloaryl compounds with long-chain alkanoyl substituents by the destannylative acylation of haloaryls bearing tri-n-butyltin (Bu3Sn) substituents. The method allows the synthesis of many important synthons for novel functional materials in a highly efficient manner. The halo-tri-n-butyltin benzenes are obtained by the lithium-halogen exchange of commercially available bis-haloarenes and the subsequent reaction with Bu3SnCl. Under typical Friedel-Crafts conditions, i.e., the presence of an acid chloride and AlCl3, the haloaryls are acylated through destannylation. The reactions proceed fast (5 min) at low temperatures and thus are compatible with aromatic halogen substituents. Furthermore, the method is applicable topara-,meta-, andortho-substitution and larger systems, as demonstrated for biphenyls. The generated tin byproducts were efficiently removed by trapping with silica/KF filtration, and most long-chain haloaryls were obtained chromatography-free. Molecular structures of several products were determined by X-ray single-crystal diffraction, and the crystal packing was investigated by mapping Hirshfeld surfaces onto individual molecules. A feasible reaction mechanism for the destannylative acylation reaction is proposed and supported through density functional theory (DFT) calculations. DFT results in combination with NMR-scale control experiments unambiguously demonstrate the importance of the tin substituent as a leaving group, which enables the acylation.
