The thiolate-for-thiolate ligand exchange reaction between the stable Au(38)(2-PET)(24) and Au(40)(2-PET)(24) (2-PET: 2-phenylethanethiol) clusters and enantiopure BINAS (BINAS: 1,1'-binaphthyl-2,2'-dithiol) was investigated by circular dichroism (CD) spectroscopy in the UV/vis and MALDI mass spectrometry (MS). The ligand exchange reaction is incomplete, although a strong optical activity is induced to the resulting clusters. The clusters are found to be relatively stable, in contrast to similar reactions on [Au(25)(2-PET)(18)](-) clusters. Maximum anisotropy factors of 6.6 × 10(-4) are found after 150 h of reaction time. During the reaction, a varying ratio between Au(38) and Au(40) clusters is found, which significantly differs from the starting material. As compared to Au(38), Au(40) is more favorable to incorporate BINAS into its ligand shell. After 150 h of reaction time, an average of 1.5 and 4.5 BINAS ligands is found for Au(38) and Au(40) clusters, respectively. This corresponds to exchange of 3 and 9 monodentate 2-PET ligands. To show that the limited exchange with BINAS is due to the bidentate nature of the ligand, exchange with thiophenol was performed. The monodentate thiophenol exchange was found to be faster, and more ligands were exchanged when compared to BINAS.

We show that MALDI mass spectrometry, suitable for mixtures, is an indispensable tool in probing the mechanism of nanocluster synthesis enabling positive identification of nanoclusters. The size evolution of the mixture of larger clusters (Au(102), Au(68), Au(38)) to form highly monodisperse Au(25) nanoclusters is demonstrated and probably includes the participation of Au(I) thiolate. The size evolution via structural reconstruction of the larger cores such as 38, approximately 44, 68, and 102 to a Au(25) nanocluster has been discussed.

Ion mobility mass spectrometry (IM-MS) can separate ions based on their size, shape, and charge as well as mass-to-charge ratios. Here, we report experimental IM-MS and IM-MS/MS data of the Au(25)(SCH(2)CH(2)Ph)(18)(-) nanocluster. The IM-MS of Au(25)(SCH(2)CH(2)Ph)(18)(-) exhibits a narrow, symmetric drift time distribution that indicates the presence of only one structure. The IM-MS/MS readily distinguishes between the fragmentation of the outer protecting layer, made from six [-SR-Au-SR-Au-SR-] "staples' where R = CH(2)CH(2)Ph, and the Au(13) core. The fragmentation of the staples is characterized by the predominant loss of Au(4)(SR)(4) from the cluster and the formation of eight distinct bands. The consecutive eight bands contain an increasing variety of Au(l)S(m)R(n)(-) product ions due to the incremental fragmentation of the outer layer of Au(21)X(14)(-), where X = S or SCH(2)CH(2)Ph. The mobility of species in each individual band shows that the lower mass species exhibit greater collision cross sections, facilitating the identification of the Au(l)S(m)R(n)(-) products. Below the bands, in the region 1200-2800 m/z, product ions relating to the fragmentation of the Au(13) core can be observed. In the low mass 50-1200 m/z region, fragment ions such as Au(SR)(2)(-), Au(2)(SR)(3)(-), Au(3)(SR)(4)(-), and Au(4)(SR)(5)(-) are also observed, corresponding to the large fragments Au(25-x)(SR)(18-(x+1)). The study shows that most of the dominant large fragments are of the general type Au(21)X(14)(-/+), and Au(17)X(10)(-/+) with electron counts of 8 and 6 in negative and positive mode, respectively. This suggests that geometric factors may outweigh electronic factors in the selection of Au(25)(SR)(18) structure.

Au144-xCux(SR)60 alloy nanomolecules were synthesized and characterized by using ESI-MS to atomic precision. A maximum of 23 copper atoms replace the gold atoms. When the number of copper atoms is higher than eight, a surface plasmon-like peak appears at ∼520 nm. Based on the fundamental elemental properties of Au and Cu, we predict a mixed atomic ordering and incorporation of Cu atoms into the Au12 and Au42 shells of the proposed icosahedral structure model of the 144-atom nanomolecule.

Au137(SR)56, a nanomolecule with a precise number of metal atoms and ligands, was synthesized. The composition was confirmed by MALDI and ESI mass spectrometry using three unique ligands (-SCH2CH2Ph, -SC6H13, and -SC4H9) and nano-alloys with Ag and Pd. The electrocatalytic properties were tested for CO2 reduction.

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We report a large surface plasmon signal amplification for a double hybridization microarray chip assembly that bridges localized gold and detection probe-carrying-core/shell Fe3O4@Au nanoparticles to enable detection of 80 aM miRNA-155 in solution.

Understanding the characteristics of nanomaterials in the context of electrode designs for bio‐electrocatalysis is an emerging research direction. Applications for fuel cells, batteries, and biosensors are directly benefited. The objective of this study is to understand the influence of unfunctionalized multiwalled carbon nanotubes (MWNT) in comparison to carboxylated nanotubes (MWNT−COOH) for pi‐pi stacking with 1‐pyrenebutyric acid (Py) and covalent immobilization of bilirubin oxidase (BOD) enzyme toward the resulting oxygen reduction currents. We designed pyrolytic graphite‐edge electrodes modified with MWNT/Py, MWNT−COOH/Py, or only MWNT−COOH for carbodiimide activation and BOD immobilization. The relative increase in surface −COOH groups as we move from MWNT to MWNT/Py to MWNT−COOH/Py modification is voltammetrically estimated. Although the MWNT−COOH/Py displayed the highest relative amount of surface −COOH groups, the oxygen reduction current was the largest for the BOD‐immobilized MWNT/Py electrode than others. Results indicate that unfunctionalized MWNT is the optimal choice for pi‐pi stacking with pyrene linkers and covalent BOD immobilization as biocathode for energy devices. Favorable hydrophobic MWNT surface to interact more closely with the electron‐receiving T1 Cu site of BOD, as opposed to the relatively polar and more defective MWNT−COOH material due to functionalization, is suggested to be one of the underlying factors for the observed electrocatalytic trend.