0000000000186076
AUTHOR
Jaakko Koivisto
Structural study of ethyl 3-arylcarbamoyl-2,3-diazabicyclo[2.2.1]hept-5-ene-2-carboxylates: conformation and transmission of substituent effects across the diazabicycloheptene ring
Nine new ethyl 3-arylcarbamoyl-2,3-diazabicyclo[2.2.1]hept-5-ene-2-carboxylates were prepared by a [4 + 2] cycloaddition and their FTIR, 1H, 13C and 15N NMR spectra were measured and assigned. Single crystals were grown for five compounds and their X-ray data were obtained. The electronic structure and the conformations were calculated by the semi-empirical AM1 method. Using correlations between the spectral, empirical and theoretical structural data, the transmission of substituent effects and the preferential conformation connected with the consecutive double nitrogen inversion and regarding the mutual orientation of NH and CO bonds were investigated. The results are compared with those f…
Photodynamics of a Molecular Water-Soluble Nanocluster Identified as Au130(pMBA)50
Photodynamics of a highly monodisperse sample of a water-soluble gold nanocluster tentatively identified as Au130(pMBA)50 (pMBA = p-mercaptobenzoic acid) was studied by mid-IR transient absorption spectroscopy with visible excitation. The observed long-lived excited states (>1 ns) indicate a molecular behavior of the cluster. By combining the transient absorption data with DFT calculation results the observed relaxation dynamics could be fully explained by identifying several relaxation processes involving singlet and triplet manifolds. The results indicate that the cluster may have interesting transient magnetic properties due to a long-lived triplet population.
Electronic and vibrational spectroscopic studies of gold-nanoclusters
Gold nanoclusters are a peculiar new material with properties between that of bulk metal and single atoms. They show size-dependent evolution of optical and electronic properties sensitive to the change of single atom or single electron in the system. Understanding the relationship between structure and properties is important to both fundamental scientific question of the role of the quantum size effects in small metal-clusters, and to application of nanoclusters in e.g. photonics, nanoelectronics, and heterogeneous catalysis. In this thesis four spectroscopic studies of monolayer-protected gold-nanoclusters are presented. The optical gap of the Au144(PET)60 and (Au/Ag)144(PET)60 (PET: pheny…
Molecule-like photodynamics of Au102(pMBA)44 nanocluster.
Photophysical properties of a water-soluble cluster Au102(pMBA)44 (pMBA = para-mercaptobenzoic acid) are studied by ultrafast time-resolved mid-IR spectroscopy and density functional theory calculations in order to distinguish between molecular and metallic behavior. In the mid-IR transient absorption studies, visible or near-infrared light is used to electronically excite the sample, and the subsequent relaxation is monitored by studying the transient absorption of a vibrational mode in the ligands. Based on these studies, a complete picture of energy relaxation dynamics is obtained: (1) 0.5-1.5 ps electronic relaxation, (2) 6.8 ps vibrational cooling, (3) intersystem crossing from the low…
Nondestructive Size Determination of Thiol-Stabilized Gold Nanoclusters in Solution by Diffusion Ordered NMR Spectroscopy
Diffusion ordered NMR spectroscopy (DOSY) was used as an analytical tool to estimate the size of thiol-stabilized gold nanoclusters in solution, namely, phenylethanethiol (PET) stabilized Au25(PET)18, Au38(PET)24, and Au144(PET)60. This was achieved by determining the diffusion coefficient and hydrodynamic radius from solution samples that were confirmed to be monodispersed by electrospray ionization mass spectrometry. The average cluster diameters obtained by this technique were estimated to be 1.7, 2.2, and 3.1 nm for the Au25(PET)18, Au38(PET)24, and Au144(PET)60 nanoclusters, respectively, which were shown to agree well with the average diameters of the corresponding single crystal or t…
Ultrafast electronic relaxation and vibrational cooling dynamics of Au 144(SC2H4Ph)60 nanocluster probed by transient mid-IR spectroscopy
Energy relaxation dynamics of a gold nanocluster with atomically precise composition, Au144(SC2H4Ph)60, is studied by transient mid-IR spectroscopy. The experiment is designed to simultaneously pro...
Site-specific targeting of enterovirus capsid by functionalized monodisperse gold nanoclusters
Development of precise protocols for accurate site-specific conjugation of monodisperse inorganic nanoparticles to biological material is one of the challenges in contemporary bionanoscience and nanomedicine. We report here a successful site-specific covalent conjugation of functionalized atomically monodisperse gold clusters with 1.5-nm metal cores to viral surfaces. Water-soluble Au102(para-mercaptobenzoic acid)44 clusters, functionalized by maleimide linkers to target cysteines of viral capsid proteins, were synthesized and conjugated to enteroviruses echovirus 1 and coxsackievirus B3. Quantitative analysis of transmission electron microscopy images and the known virus structures showed …
Electron microscopy of gold nanoparticles at atomic resolution
Detailed structure of a gold nanoparticle Adding only a few atoms or changing the capping ligand can dramatically change the structure of individual metal nanoparticles. Azubel et al. used aberration-corrected transmission electron microscopy to derive a three-dimensional reconstruction of water-soluble gold nanoparticles. Small-angle x-ray scattering and other techniques have also corroborated this model. They used this to determine the atomic structure, which compared favorably with density functional theory calculations, without assuming any a priori structural knowledge or the use of model fitting. Science , this issue p. 909
Electronic and vibrational signatures of the Au102p-MBA44 cluster
Optical absorption of a gold nanocluster of 102 Au atoms protected by 44 para-mercaptobenzoic acid (p-MBA) ligands is measured in the range of 0.05-6.2 eV (mid-IR to UV) by a combination of several techniques for purified samples in solid and solution phases. The results are compared to calculations for a model cluster Au(102)(SMe)(44) based on the time-dependent density functional theory in the linear-response regime and using the known structure of Au(102)(p-MBA)(44). The measured and calculated molar absorption coefficients in the NIR-vis region are comparable, within a factor of 2, in the absolute scale. Several characteristic features are observed in the absorption in the range of 1.5-…
Acid–Base Properties and Surface Charge Distribution of the Water-Soluble Au102(pMBA)44 Nanocluster
The pKa of the p-mercaptobenzoic acid (pMBA) ligands in the Au102(pMBA)44 nanocluster was measured by using acid–base and IR titration. The observed macroscopic pKa = 6.18 ± 0.05 is significantly more basic than that of free pMBA (pKa = 4.16), and the protonation behavior is anticooperative according to the Hill coefficient n = 0.64 ± 0.04. The cluster is truly water-soluble when more than 22 and insoluble when fewer than 7 ligands are in the deprotonated state. In order to obtain more insight into the anticooperative character, the cluster was modeled at pH ∼6.2 using constant pH molecular dynamics simulations. The pKa values of the individual pMBAs are in the range of 5.18–7.58, depending…
Solvation chemistry of water-soluble thiol-protected gold nanocluster Au102 from DOSY NMR spectroscopy and DFT calculations
The hydrodynamic diameter of Aum(pMBA)n [(m, n) = (102, 44) and (144, 60)] clusters in aqueous media was determined via DOSY NMR spectroscopy. The apparent size of the same (n, m) cluster depends on the counter ion of the deprotonated pMBA− ligand as explained by the competing ion-pair strength and hydrogen bonding interactions studied in DFT calculations. The choice of the counter ion affects the surface chemistry and molecular structure at the organic/water interface, which is relevant for biological applications.
Vibrational Perturbations and Ligand–Layer Coupling in a Single Crystal of Au144(SC2H4Ph)60 Nanocluster
We have determined vibrational signatures and optical gap of the Au144(PET)60 (PET: phenylethylthiol, SC2H4Ph) nanocluster solvated in deuterated dichloromethane (DCM-D2, CD2Cl2) and in a single crystal. For crystals, solid-state (13)C NMR and X-ray diffraction were also measured. A revised value of 2200 cm(-1) (0.27 eV) was obtained for the optical gap in both phases. The vibrational spectra of solvated AU144(PET)60 closely resembles that of neat PET, while the crystalline-state spectrum exhibits significant inhomogeneous spectral broadening, frequency shifts, intensity transfer between vibrational modes, and an increase in the overtone and combination transition intensities. Spectral broa…