Rigid Single Carbon–Carbon Bond That Does Not Rotate in Water

Carbon–carbon bond is one of the most ubiquitous molecular building blocks for natural and man-made materials. Rotational isomerization is fundamentally important for understanding the structure and reactivity of chemical and biological molecules. Reported herein is the first demonstration that a single C–C bond does not rotate in water. The two distal C–S bonds in both 1,2-ethanedithiolate (⁻S–CH₂–CH₂–S^–, 1,2-EDT^2–) and 2,3-butanedithiolate (2,3-BuDT^2–) are exclusively in the <i>trans</i> conformer with reference to their respective center single C–C bond. In contrast, both <i>trans</i> and <i>gauche</i> conformers are observed in neutral 1,2-ethanedithiol (1,2-EDT) and 2, 3-butanedithiol (2,3-BuDT). The insight from this work should be important for understanding the charge effect on the molecular conformation in aqueous solutions

Exposure to Bisphenol A, Bisphenol F, and Bisphenol S in U.S. Adults and Children: The National Health and Nutrition Examination Survey 2013–2014

Bisphenol F (BPF) and bisphenol S (BPS) are replacing bisphenol A (BPA) in the manufacturing of products containing polycarbonates and epoxy resins. Data on current human exposure levels of these substitutes are needed to aid in the assessment of their human health risks. This study analyzed urinary bisphenol levels in adults (<i>N</i> = 1808) and children (<i>N</i> = 868) participating in the National Health and Nutrition Examination Survey (NHANES) 2013–2014 and investigated demographic and lifestyle factors associated with urinary levels of bisphenols. BPA, BPS, and BPF were detected in 95.7, 89.4, and 66.5% of randomly selected urine samples analyzed as part of NHANES 2013–2014, respectively. Median levels of BPA in U.S. adult were higher (1.24 μg/L) than BPF and BPS levels (0.35 and 0.37 μg/L, respectively). For children, median BPA levels were also higher (1.25 μg/L) than BPF and BPS levels (0.32 and 0.29 μg/L, respectively). The limits of detection for BPA, BPF, and BPS were 0.2, 0.2, and 0.1 μg/L, respectively. Urinary levels showed associations with gender, race/ethnicity, family income, physical activity, smoking, and/or alcohol intake that depended on the specific bisphenol. The results of this study indicate that exposure of the general U.S. population to BPA substitutes is almost ubiquitous. Because exposures differ across the U.S. population, further studies of environmental, consumer, and lifestyle factors affecting BPF and BPS exposures are warranted

Reactive Ag⁺ Adsorption onto Gold

Proposed mechanisms of monolayer silver formation on gold nanoparticle (AuNP) include AuNP-facilitated under-potential reduction and antigalvanic reduction in which the gold reduces Ag⁺ into metallic atoms Ag(0). Reported herein is the spontaneous reactive Ag⁺ adsorption onto gold substrates that include both as-obtained and butanethiol-functionalized citrate- and NaBH₄-reduced gold nanoparticles (AuNPs), commercial high-purity gold foil, and gold film sputter-coated onto silicon. The silver adsorption invariably leads to proton releasing to the solution. The nominal saturation packing density of silver on AuNPs varies from 2.8 ± 0.3 nmol/cm² for the AuNPs preaggregated with KNO₃ to 4.3 ± 0.2 nmol/cm² for the AuNPs prefunctionalized with butanethiol (BuT). The apparent Langmuir binding constant of the Ag⁺ with the preaggregated AuNPs and BuT-functionalized AuNPs are 4.0 × 10³ M^–1 and 2.1 × 10⁵ M^–1, respectively. The silver adsorption has drastic effects on the structure, conformation, and stability of the organothiols on the AuNPs. It converts disordered BuT on AuNPs into highly ordered <i>trans</i> conformers, but induces near complete desorption of sodium 2-mercaptoethanesulfonate and sodium 3-mercapto-1-propyl sulfonate from AuNPs. Mechanically, the Ag⁺ adsorption on AuNPs most likely proceeds by reacting with molecules preadsorbed on the AuNP surfaces or chemical species in the solutions, and the silver remains as silver ion in these reaction products. This insight and methodology presented in this work are important for studying interfacial interactions of metallic species with gold and for postpreparation modulation of the organothiol structure and conformation on AuNP surfaces

Comparative Study of the Self-Assembly of Gold and Silver Nanoparticles onto Thiophene Oil

Nanoparticle self-assembly is fundamentally important for bottom-up functional device fabrication. Currently, most nanoparticle self-assembly has been achieved with gold nanoparticles (AuNPs) functionalized with surfactants, polymeric materials, or cross-linkers. Reported herein is a facile synthesis of gold and silver nanoparticle (AgNP) films assembled onto thiophene oil by simply vortex mixing neat thiophene with colloidal AuNPs or AgNPs for ∼1 min. The AuNP film can be made using every type of colloidal AuNPs we have explored, including sodium borohydride-reduced AuNPs with a diameter of ∼5 nm, tannic acid-reduced AuNPs of ∼10 nm diameter, and citrate-reduced AuNPs with particle sizes of ∼13 and ∼30 nm diameter. The AuNP film has excellent stability and it is extremely flexible. It can be stretched, shrunken, and deformed accordingly by changing the volume or shape of the enclosed thiophene oil. However, the AgNP film is unstable, and it can be rapidly discolored and disintegrated into small flakes that float on the thiophene surface. The AuNP and AgNP films prepared in the glass vials can be readily transferred to glass slides and metal substrates for surface-enhanced Raman spectral acquisition

Comparative Study of the Self-Assembly of Gold and Silver Nanoparticles onto Thiophene Oil

Nanoparticle self-assembly is fundamentally important for bottom-up functional device fabrication. Currently, most nanoparticle self-assembly has been achieved with gold nanoparticles (AuNPs) functionalized with surfactants, polymeric materials, or cross-linkers. Reported herein is a facile synthesis of gold and silver nanoparticle (AgNP) films assembled onto thiophene oil by simply vortex mixing neat thiophene with colloidal AuNPs or AgNPs for ∼1 min. The AuNP film can be made using every type of colloidal AuNPs we have explored, including sodium borohydride-reduced AuNPs with a diameter of ∼5 nm, tannic acid-reduced AuNPs of ∼10 nm diameter, and citrate-reduced AuNPs with particle sizes of ∼13 and ∼30 nm diameter. The AuNP film has excellent stability and it is extremely flexible. It can be stretched, shrunken, and deformed accordingly by changing the volume or shape of the enclosed thiophene oil. However, the AgNP film is unstable, and it can be rapidly discolored and disintegrated into small flakes that float on the thiophene surface. The AuNP and AgNP films prepared in the glass vials can be readily transferred to glass slides and metal substrates for surface-enhanced Raman spectral acquisition

Studying the Effects of Cysteine Residues on Protein Interactions with Silver Nanoparticles

Studies of protein and organothiol interactions with silver nanoparticles (AgNPs) are important for understanding AgNP nanotoxicity, antimicrobial activity, and material fabrications. Reported herein is a systematic investigation of the effects of both reduced and oxidized protein cysteine residues on protein interactions with AgNPs. The model proteins included wild-type and mutated protein GB3 variants that contain 0, 1, or 2 reduced cysteine residues, respectively. Bovine serum albumin (BSA) that contains a total of 34 oxidized (disulfide-linked) cysteine residues and one reduced cysteine residue was also included. Protein cysteine content has no detectable effect on the kinetics of protein/AgNP binding. However, only proteins that contain reduced cysteine residues induce significant AgNP dissolution. Proteins can slow down, but do not prevent the AgNP dissolution induced by subsequently added organothiols. The insights provided in this work are important to the mechanistic understanding of AgNP stability in biofluids that are rich in proteins and amino acid thiols

Ion Pairing as the Main Pathway for Reducing Electrostatic Repulsion among Organothiolate Self-assembled on Gold Nanoparticles in Water

Organothiol binding to gold nanoparticles (AuNPs) in water proceeds through a deprotonation pathway in which the sulfur-bound hydrogen (RS-H) atoms are released to solution as protons and the organothiol attach to AuNPs as negatively charged thiolate. The missing puzzle pieces in this mechanism are (i) the significance of electrostatic repulsion among the likely charged thiolates packed on AuNP surfaces, and (ii) the pathways for the ligand binding system to cope with such electrostatic repulsion. Presented herein are a series of experimental and theoretical evidence that ion pairing, the coadsorption of negatively charged thiolate and positively charged cations, is a main mechanism for the system to reduce the electrostatic repulsion among the thiolate self-assembled onto AuNP surfaces. This work represents a significant step forward in the comprehensive understanding of organothiol binding to AuNPs

Structures and Conformations of Alkanedithiols on Gold and Silver Nanoparticles in Water

Organodithiols with two distal thiols have been used extensively in gold and silver nanoparticle (AuNP and AgNP) applications. However, understanding the structures and conformations of organodithiols on these nanoparticles is challenging. Reported in this work is a combined surface enhanced Raman spectroscopy (SERS), transmission electron microscope (TEM), inductively coupled plasma mass-spectrometry (ICP-MS), and localized surface plasmonic resonance (LSPR) study of alkyldithiol (ADT, (HS-(CH₂)_<i>n</i>-SH, <i>n</i> = 2, 4, and 6) interactions with AuNPs and AgNPs in water. These complementary techniques revealed a series of new insights that would not be possible using individual methods. A large-fraction of ADTs lies flat on AuNP surfaces. The upright ADTs are dimerized horizontally through disulfide-bond, or remain as monothiolates on the AuNP surfaces. The possibility of a significant amount of vertically disulfide-linked organodithiol on the surface is excluded on the basis of ICP-MS and AuNP LSPR experiments. ADTs induced significant AgNP disintegrations in which ADTs are predominantly in dithiolate forms. This work highlights the extraordinary complexity of organodithiol interactions with plasmonic nanoparticles. The insights provided in this work will be important for enhancing fundamental understanding of the structure and properties of organothiol-functionalized AgNPs and AuNPs

Ligand Adsorption and Exchange on Pegylated Gold Nanoparticles

Previous researchers proposed that thiolated poly­(ethylene glycol) (PEG-SH) adopts a “mushroom-like” conformation on gold nanoparticles (AuNPs) in water. However, information regarding the size and permeability of the PEG-SH mushroom caps and surface area passivated by the PEG-SH mushroom stems are unavailable. Reported herein is our finding that AuNPs that are covered by saturation packed PEG-SHs all have large fractions of AuNP surface area available for ligand adsorption and exchange. The model ligands adenine and 2-mercaptobenzimidazole (2-MBI) can rapidly penetrate the PEG-SH overlayer and adsorb onto the AuNP surface. Most of the ligand adsorption and exchange occurs within the first minutes of the ligand addition. The fraction of AuNP surface area passivated by saturation packed model PEG-SHs are ∼25%, ∼20%, and ∼9% for PEG-SHs with molecular weights of 2000, 5000, and 30 000 g/mol, respectively. Localized surface plasmonic resonance and dynamic light scattering show that the PEG-SH overlayer is drastically more loosely packed than the protein bovine serum albumin on AuNPs. Studies investigating the effect of aging the AuNP/PEG-SH mixtures on subsequent adenine adsorption onto the pegylated AuNPs revealed that PEG-SHs reach approximately a steady-state binding on AuNPs within 3 h of sample incubation. This work sheds new insights into the kinetics, structures, and conformations of PEG-SHs on AuNPs and demonstrates that pegylated AuNPs can be used as an important platform for studying ligand interaction with AuNPs. In addition, it also opens a new avenue for fabrication of multicomponent functionalized nanoparticles