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51.
Vinayak Juvekar Chang Su Lim Dong Joon Lee Sang Jun Park Gyeong Ok Song Hyuk Kang Hwan Myung Kim 《Chemical science》2021,12(1):427
Two-photon photodynamic therapy (TP-PDT) is a promising approach for the treatment of cancer because of its better penetration depth and superior spatial selectivity. Here, we describe an azo group containing cyclized-cyanine derivatives (ACC1 and ACC2) as a two-photon activated, type I based photosensitizer (PS). These small-molecule and heavy atom-free organic dyes showed marked reactive oxygen species (ROS)-generating ability under physiological conditions, as well as fast loading ability into the cells and negligible dark toxicity. Live cell analyses with one- and two-photon microscopy revealed that these dyes showed higher ROS generation ability upon two-photon excitation than upon one-photon excitation via the type I process. The PSs have superior PDT properties compared to conventional Visudyne and 5-ALA under mild conditions. These characteristics allowed for precise PDT at the target region in mimic tumor spheroids, demonstrating that the developed TP PS could be useful in efficient PDT applications and in designing various PSs.Azo containing dyes as a two-photon selective and type I based photosensitizers (PSs) were developed that exhibit excellent photodynamic therapy properties under mild condition. 相似文献
52.
We report microscopic observations and a structural determination of actin granules self-assembled in concentrated solutions of actin filaments (F-actin). Optical microscopy shows reproducible formation of numerous and stable granules of densely packed F-actin of variable sizes on the order of 10 microm. These granules coexist with a uniform network of F-actin of a lower concentration. The microscopic segregation of F-actin into two distinct states is assisted by an actin cross-linking protein, alpha-actinin. The rapid on and off rates and temperature sensitivity of the alpha-actinin/F-actin interaction facilitate the formation of multi-micrometer-sized granules of well-defined shapes. Additional physical factors such as the excluded volume effect and the minimization of surface energy act in concert with the specific molecular interactions to define the intriguing granular formation. Both the biochemical specificity of alpha-actinin and the thermodynamics of phase transitions are required for understanding such large scale self-assembly. 相似文献
53.
The synthesis of extended dicationic bis-benzimidazoles starting from trans-1,2-bis(4-cyanophenyl)ethene and trans-1,2-bis(4-cyanophenyl)cyclopropane is reported. The target diamidines show significant in vitro activity against B. subtilis. 相似文献
54.
Kang YK Rubtsov IV Iovine PM Chen J Therien MJ 《Journal of the American Chemical Society》2002,124(28):8275-8279
The electron-transfer (ET) dynamics of a series of unusually rigid pi-stacked porphyrin-quinone (P-Q) systems, in which sub-van der Waals interplanar distances separate juxtaposed porphyryl, aromatic bridge, and quinonyl components of these assemblies, are reported. The photoinduced charge separation (CS) and thermal charge recombination (CR) ET reactions of [5-[8'-(2',5'-benzoquinonyl)-1'-naphthyl]-10,20-diphenylporphinato]zinc(II) (1a-Zn), [5-[8'-(4'-[8'"-(2'"',5'"'-benzoquinonyl)-1'"-naphthyl]-1'-phenyl)-1'-naphthyl]-10,20-diphenylporphinato]zinc(II) (2a-Zn), and [5-(8'-[4'-(8'"-[4'"'-(8'"-[2'"',5'"'-benzoquinonyl]-1'"-naphthyl)-1'"'-phenyl]-1'"-naphthyl)-1'-phenyl]-1'-naphthyl)-10,20-diphenylporphinato]zinc(II) (3a-Zn) in CH(2)Cl(2) were investigated by pump-probe transient absorption spectroscopy. Analyses of these data show that the phenomenological ET distance dependence (beta) for both the CS and CR reactions in these systems is soft (beta(CS) = 0.43 A(-1); beta(CR) = 0.35 +/- 0.16 A(-1)). This work demonstrates that simple aromatic building blocks such as benzene, which are characterized by highly stabilized filled molecular orbitals and large HOMO-LUMO gaps, can provide substantial D-A electronic coupling when organized within a pi-stacked structural motif that features a modest degree of arene-arene interplanar compression. 相似文献
55.
A series of tetranuclear Mo(W)-Ag mixed-metal clusters have been synthesized by making use of the solid state reactions of [NH4]2[MYS3](M= Mo, W; Y= O, S), AgX(X= Cl, Br, I) and (n-Bu)4NX' (X' =Cl, Br), two of which [(n-Bu)4N]3[MoOS3Ag3Br4] (1) and [(n-Bu)4N]3[WS4Ag3Cl4] ( 2 ) have been structurally characterized by X-ray analysis. The crystal data: 1 , cubic, P4 3m, αequals;12.093(4) Å, Z=1, R =0.076; 2 , cubic, P4 3m, αequals;12.059(2) Å, Z =1, R =0.075. The cluster anion core [Ag3MS3X'] of the two compounds can be viewed as a cube in which the four metal atoms and the four non-metal atoms are statistically distributed, respectively. Substitution reaction with PPh3 ligand is also discussed for this type of tetranuclear clusters. 相似文献
56.
Fluorescein has an extremely low luminescence intensity in acidic aqueous media. However, when it was bound to proteins, subsequent increase of luminescence intensity took place. Furthermore, when a hydrophobic tail, such as aliphatic hydrocarbons, was introduced to fluorescein, more dramatic increase of luminescence intensity was observed upon binding to proteins. In the present study, by utilizing this luminescence enhancement, three hydrophobic fluorescein dyes (5-dodecanoyl amino fluorescein, 5-hexadecanoyl amino fluorescein, and 5-octadecanoyl amino fluorescein) were examined as noncovalent fluorescent stains of protein bands in sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE). Effective incorporation of the dyes to proteins in gels was accomplished either simply by adding dyes at the protein fixation step, or by treating gels with a staining solution after the fixation. The sensitivity of this staining method using the fluorescein derivatives was approximately 1 ng/band for most proteins. For some cases, protein bands containing as low as 0.1 ng were successfully visualized. In addition, the detection sensitivity showed much less protein-to-protein variation than silver staining. This new staining method was also successfully applied to two-dimensional electrophoresis of rat brain proteins. Its overall sensitivity was comparable to that of silver staining. 相似文献
57.
Jung-Ah Kang Ji-Sun Kwak Sang-Heon Park Kyu-Young Sim Seul Ki Kim Youngnim Shin In Jung Jung Jeong-In Yang Jang-Soo Chun Sung-Gyoo Park 《Experimental & molecular medicine》2021,53(4):560
Zinc is a trace element that is essential for immune responses. Therefore, changes in cellular zinc levels in specific immune cells may influence inflammatory autoimmune diseases, such as rheumatoid arthritis (RA). However, the regulation of zinc mobilization in immune cells and its role in the pathogenesis of RA are not fully understood. Thus, we investigated the roles of zinc transporters in RA pathogenesis. We demonstrated that ZIP8 was specifically upregulated in CD4+ T cells that infiltrated the inflamed joint and that ZIP8 deficiency in CD4+ T cells abrogated collagen-induced arthritis. ZIP8 deficiency dramatically affected zinc influx in effector T cells and profoundly reduced T cell receptor (TCR)-mediated signaling, including NF-κB and MAPK signaling, which are pathways that are involved in T helper (Th) 17 cell differentiation. Taken together, our findings suggest that ZIP8 depletion in CD4+ T cells attenuates TCR signaling due to insufficient cellular zinc, thereby reducing the function of effector CD4+ T cells, including Th17 cells. Our results also suggest that targeting ZIP8 may be a useful strategy to inhibit RA development and pathogenesis.Subject terms: Autoimmunity, Immunological disorders 相似文献
58.
D. W. Kang G. P. Rajendran M. Zeldin 《Journal of polymer science. Part A, Polymer chemistry》1986,24(6):1085-1095
The thermal degradation of Me3SiO end-blocked polydimethylsiloxane (eb-PDMS) and polydimethylsiloxane-N-phenylsilazane (eb-PDMS–NPhSz) copolymer was studied. For both polymers relative degree of polymerization (DP /DP 0) as a function of conversion (1 – W/W0) data were obtained. For eb-PDMS the results were consistent with a mechanism involving a rate determining random siloxane bond cleavage initiation step followed by a rapid and complete depropagation of the active fragments evolving volatile cyclic oligomers. Rate constants (k) for initiation were obtained at four temperatures from plots of DP ?1 vs. time. An Arrhenius activation energy of approximately 80 kcal/mol was determined and is consistent with a SiOSi scission transition state. The degradation of eb-PDMS–NPhSz appears to follow the same depolymerization process evolving cyclic oligomers. Although DP /DP 0 vs. C data suggest a random cleavage–complete depolymerization mechanism, an Arrhenius plot suggests a more complex degradation mechanism. The role of impurities as degradation catalysts is discussed. 相似文献
59.
Jian-Ping Lang Guo-Qing Bian Jin-Hua Cai Bei-Sheng Kang Xin-Quan Xin 《Transition Metal Chemistry》1995,20(4):376-379
Summary Reaction of [NH4]2[WS4] with CuX (X = Cl or I) and R4NX (R = Et or n-Bu) in the solid state gave two new bimetallic compounds with W:Cu compositions from 1:3 to 1:4. Compound (1), [(n-Bu)4N]3[WS4Cu3Cl3Br], crystallizes in the hexagonal space group R3c with a = 17.051(5), c = 38.372(5) Å, V = 9661.8 Å3, Z = 6. The cluster anion of (1) comprises a cubane-like cluster core [WS3Cu3Br] of C3 symmetry with a Cl atom attached to each of the three Cu atoms and one terminal sulphido ligand attached to the W atom. Compound (2), [Et4N]4[WS4Cu4I6], crystallizes in the monoclinic space group C2/m with a = 29.702(6), b = 12.7887(5), c = 15.327(3)Å, = 99.69(2), V = 5738.1 Å3, Z = 4. In the cluster anion of (2), four edges of the WS4 core are coordinated by four Cu atoms, giving a WS4Cu4 aggregate of approximate C2V symmetry. 相似文献
60.
As a new type of foldamers, oligoindoles containing 4, 6, and 8 indole rings were synthesized, and their folding properties were characterized by a combination of 1H NMR techniques and UV/visible titration experiments. When chloride was added, the NH signals of the oligoindoles were downfield shifted as a result of hydrogen-bond formation, and the aromatic signals were upfield shifted by stacking between two indoles. Moreover, the ROESY experiment provided definitive NOE evidence for the helical stacking in the presence of chloride. Finally, the UV/visible titration experiments demonstrated that the oligoindoles formed 1:1 complexes with chloride, and the association constants greatly increased with increasing the number of the indole NHs. These observations are all consistent with the fact that oligoindoles adopt a helical conformation when complexed with chloride by hydrogen-bonding interactions. 相似文献