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排序方式: 共有214条查询结果,搜索用时 343 毫秒
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Verdoes M Florea BI van der Linden WA Renou D van den Nieuwendijk AM van der Marel GA Overkleeft HS 《Organic & biomolecular chemistry》2007,5(9):1416-1426
The synthesis and evaluation of hybrid proteasome inhibitors that contain structural elements of the known inhibitors bortezomib, epoxomicin and peptide vinyl sulfones is described. From the panel of 15 inhibitors some structure activity relationships can be deduced with regard to inhibitory activity in relation to peptide recognition element, inhibitor size and nature of the electrophilic trap. Further, the panel contains one of the most potent peptide-based pan-proteasome inhibitors reported to date. 相似文献
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Hetterscheid DG Klop M Kicken RJ Smits JM Reijerse EJ de Bruin B 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(12):3386-3405
A series of new metalloradical rhodium and iridium complexes [M(II)(cod)(N-ligand)](2+) in the uncommon oxidation state +II were synthesized by one-electron oxidation of their [M(I)(cod)(N-ligand)](+) precursors (M=Rh, Ir; cod=(Z,Z)-1,5-cyclooctadiene; and N-ligand is a podal bis(pyridyl)amine ligand: N,N-bis(2-pyridylmethyl)amine (dpa), N-(2-pyridylmethyl)-N-(6-methyl-2-pyridylmethyl)amine (pla), or N-benzyl-N,N-bis(6-methyl-2-pyridylmethyl)amine (Bn-dla). EPR spectroscopy, X-ray diffraction, and DFT calculations reveal that each of these [M(II)(cod)(N-ligand)](2+) species adopts a square-pyramidal geometry with the two cod double bonds and the two pyridine fragments in the basal plane and the N(amine) donor at the apical position. The unpaired electron of these species mainly resides at the metal center, but the apical N(amine) donor also carries a considerable fraction of the total spin density (15-18 %). Density functional calculations proved a valuable tool for the analysis and simulation of the experimental EPR spectra. Whereas the M(II)(olefin) complexes are quite stable as solids, in solution they spontaneously transform into a 1:1 mixture of M(III)(allyl) species and protonated M(I)(olefin) complexes (in the forms [M(I)(olefin)(protonated N-ligand)](2+) for M=Rh and [M(III)(H)(olefin)(N-ligand)](2+) for M=Ir). Similar reactions were observed for the related propene complex [M(II)(propene)(Me(2)tpa)](2+) (Me(2)tpa=N,N,N-tris(6-methyl-2-pyridylmethyl)amine). The decomposition rate of the [M(II)(cod)(N-ligand)](2+) species decreases with increasing N-ligand bulk in the following order: dpa>pla>Bn-dla. Decomposition of the most hindered [M(II)(cod)(Bn-dla)](2+) complexes proceeds by a second-order process. The kinetic rate expression v=k(obs)[M(II)](2) in acetone with k(obs)=k'[H(+)][S], where [S] is the concentration of additional coordinating reagents (MeCN), is in agreement with ligand-assisted dissociation of one of the pyridine donors. Solvent coordination results in formation of more open, reactive species. Protonation of the noncoordinating pyridyl group increases the concentration of this species, and thus [H(+)] appears in the kinetic rate expression. The kinetic data are in agreement with bimolecular hydrogen-atom transfer from M(II)(cod) to another M(II) species (DeltaH( not equal)=11.5+/-2 kcal mol(-1), DeltaS( not equal)=-27+/-10 cal K(-1) mol(-1), and DeltaG( not equal)(298 K)=19.5+/-5 kcal mol(-1)). 相似文献
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Protonation of a Biologically Relevant CuII μ‐Thiolate Complex: Ligand Dissociation or Formation of a Protonated CuI Disulfide Species?
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Erica C. M. Ording‐Wenker Martijn van der Plas Dr. Maxime A. Siegler Dr. Célia Fonseca Guerra Prof. Dr. Elisabeth Bouwman 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(51):16913-16921
The proton‐induced electron‐transfer reaction of a CuII μ‐thiolate complex to a CuI‐containing species has been investigated, both experimentally and computationally. The CuII μ‐thiolate complex [CuII2( LMeS )2]2+ is isolated with the new pyridyl‐containing ligand LMeSSLMe , which can form both CuII thiolate and CuI disulfide complexes, depending on the solvent. Both the CuII and the CuI complexes show reactivity upon addition of protons. The multivalent tetranuclear complex [CuI2CuII2( LS )2(CH3CN)6]4+ crystallizes after addition of two equivalents of strong acid to a solution containing the μ‐thiolate complex [CuII2( LS )2]2+ and is further analyzed in solution. This study shows that, upon addition of protons to the CuII thiolate compound, the ligand dissociates from the copper centers, in contrast to an earlier report describing redox isomerization to a CuI disulfide species that is protonated at the pyridyl moieties. Computational studies of the protonated CuII μ‐thiolate and CuI disulfide species with LSSL show that already upon addition of two equivalents of protons, ligand dissociation forming [CuI(CH3CN)4]+ and protonated ligand is energetically favored over conversion to a protonated CuI disulfide complex. 相似文献
126.
Maarten Honing Chris Martini Monique van Velzen Marieke Niesters Albert Dahan Martijn Boon 《Molecules (Basel, Switzerland)》2020,25(24)
General anesthesia is obtained by administration of potent hypnotics, analgesics and muscle relaxants. Apart from their intended effects (loss of consciousness, pain relief and muscle relaxation), these agents profoundly affect the control of breathing, in part by an effect within the peripheral chemoreflex loop that originates at the carotid bodies. This review assesses the role of cholinergic chemotransmission in the peripheral chemoreflex loop and the mechanisms through which muscle relaxants and hypnotics interfere with peripheral chemosensitivity. Additionally, consequences for clinical practice are discussed. 相似文献
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In this study, the phenomenon of higher harmonic thickness resonance of a piezoelectric transducer was used to investigate potentially additional sensitivity at the third harmonic frequency for conventional medical transducers. The motivation for this research is that some applications in medical ultrasound (e.g. third harmonic transmit phasing and contrast imaging) need probes which are sensitive around both the fundamental and third harmonic frequencies, and that these higher harmonic thickness modes, although often considered as undesired, might be used beneficially. The novelty aspect in this study is the presented transmit and receive potential at both the fundamental and third harmonic of a conventional cardiac probe with modified electrical tuning. Elements of an experimental PZT-based phased-array probe (fc = 3 MHz, 64 elements, element width = 0.3 mm, elevation aperture = 13 mm) were electrically retuned with series inductors around the third harmonic resonance frequency at 10 MHz. Hydrophone measurements with 10-MHz-tuned elements showed that, as compared to a conventionally tuned element, the transmit transfer function at the third harmonic increased more than 23 dB, while the sensitivity at the fundamental frequency was only 6 dB lower. Pulse-echo measurements showed that the two-way transfer function of a 10-MHz-tuned element resulted in 20 dB increased sensitivity around the third harmonic as compared to an untuned element. Simulated transfer functions, from both a 1D KLM and 2D finite element model of an element of the experimental array transducer, confirmed the measured sensitivity peaks at the fundamental and third harmonic. In conclusion, this study demonstrated the effect of changing the electrical tuning on a conventional array transducer which increased the sensitivity around the third harmonic resonance frequency, while maintaining good sensitivity at the fundamental frequency. 相似文献
130.
Triesscheijn M Ruevekamp M Antonini N Neering H Stewart FA Baas P 《Photochemistry and photobiology》2006,82(6):1686-1690
Meso-tetra-hydroxyphenyl-chlorin (mTHPC)-mediated photodynamic therapy (PDT) has shown to be effective in the treatment of patients with multiple basal cell carcinoma (BCC). In the present study we further optimized the drug-light interval and examined the correlation between plasma drug levels and treatment efficacy. Thirteen patients with multiple BCC (a total of 366 lesions) were included in the study. Following intravenous administration of 0.1 mg kg(-1) mTHPC, lesions were illuminated with 10 J cm(-2) light (652 nm, 100 mW cm(-2)) at 12, 24, 48, 72 or 96 h. Plasma samples were taken prior to each illumination for determination of mTHPC levels, and tumor response was evaluated at 6 months and 1 year. Both univariable and multivariable analyses showed that optimal treatment outcome was obtained for a drug-light interval of 24 h when plasma drug levels were high. Overall, good cosmetic results with little or no scarring were obtained in 87% of the treated lesions and no serious side effects were observed. We optimized mTHPC-mediated PDT for patients suffering from multiple BCC by determining the most effective drug-light interval and showed that this treatment offers significant advantages over surgical resection. 相似文献