Evaluation of Thiol Raman Activities and pKa Values using Internally Referenced Raman-based pH Titration

Thiols are one of the most important classes of chemicals used broadly in organic synthesis, biological chemistry, and nanosciences. Thiol pKa values are key indicators of thiol reactivity and functionality. This study is an internally-referenced Raman-based pH titration method that enables reliable quantification of thiol pKa values for both mono- and di-thiols in water. The degree of thiol ionization is monitored directly using the peak intensity of the S-H stretching feature relative to an internal reference peak as a function of solution pH. The thiol pKa values and Raman activity relative to its internal reference were then determined by curveitting the experimental data with equations derived on the basis of the Henderson-Hasselbalch equation. Using this Raman titration method, first and second thiol pKa values for 1,2-benzenedithol in water were determined for the first time. This method is convenient to implement and its underlying theory is easy to follow

Evaluation of Thiol Raman Activities and pKa Values using Internally Referenced Raman-based pH Titration

Thiols are one of the most important classes of chemicals used broadly in organic synthesis, biological chemistry, and nanosciences. Thiol pKa values are key indicators of thiol reactivity and functionality. This study is an internally-referenced Raman-based pH titration method that enables reliable quantification of thiol pKa values for both mono- and di-thiols in water. The degree of thiol ionization is monitored directly using the peak intensity of the S-H stretching feature relative to an internal reference peak as a function of solution pH. The thiol pKa values and Raman activity relative to its internal reference were then determined by curveitting the experimental data with equations derived on the basis of the Henderson-Hasselbalch equation. Using this Raman titration method, first and second thiol pKa values for 1,2-benzenedithol in water were determined for the first time. This method is convenient to implement and its underlying theory is easy to follow

Carbon disulfide. Just toxic or also bioregulatory and/or therapeutic?

The overview presented here has the goal of examining whether carbon disulfide (CS2) may play a role as an endogenously generated bioregulator and/or has therapeutic value. The neuro- and reproductive system toxicity of CS2 has been documented from its long-term use in the viscose rayon industry. CS2 is also used in the production of dithiocarbamates (DTCs), which are potent fungicides and pesticides, thus raising concern that CS2 may be an environmental toxin. However, DTCs also have recognized medicinal use in the treatment of heavy metal poisonings as well as having potency for reducing inflammation. Three known small molecule bioregulators (SMBs) nitric oxide, carbon monoxide, and hydrogen sulfide were initially viewed as environmental toxins. Yet each is now recognized as having intricate, though not fully elucidated, biological functions at concentration regimes far lower than the toxic doses. The literature also implies that the mammalian chemical biology of CS2 has broader implications from inflammatory states to the gut microbiome. On these bases, we suggest that the very nature of CS2 poisoning may be related to interrupting or overwhelming relevant regulatory or signaling process(es), much like other SMBs

Contradictory Dual Effects: Organothiols Can Induce Both Silver Nanoparticle Disintegration and Formation under Ambient Conditions

Using propanethiol (PrT), 2-mercaptoethanol (ME), glutathione (GSH), and cysteine (Cys) as model thiols, we demonstrated herein that organothiols can induce both silver nanoparticle (AgNP) disintegration and formation under ambient conditions by simply mixing organothiols with AgNPs and AgNO₃, respectively. Mechanistically, organothiols induce AgNP disintegration by chelating silver ions produced by ambient oxygen oxidizing the AgNPs, while AgNP formation in AgNO₃/organothiol mixtures is the result of organothiols serving as the reducing agent. Furthermore, surface-plasmon- and fluorescent-active AgNPs can be interconverted by adding excess Ag⁺ or ME into the AgNP-containing solutions. Organothiols can also reduce gold ion in HAuCl₄/organothiol solutions into fluorescence- and surface-plasmon-active gold nanoparticles (AuNPs), but no AuNP disintegration occurs in the AuNP/organothiol solutions. This work highlights the extraordinary complexity of organothiol interactions with gold and silver nanoparticles. The insights from this work will be important for AgNP and AuNP synthesis and applications

Hole extraction by design in photocatalytic architectures interfacing CdSe quantum dots with topochemically stabilized tin vanadium oxide

Tackling the complex challenge of harvesting solar energy to generate energy-dense fuels such as hydrogen requires the design of photocatalytic nanoarchitectures interfacing components that synergistically mediate a closely interlinked sequence of light-harvesting, charge separation, charge/mass transport, and catalytic processes. The design of such architectures requires careful consideration of both thermodynamic offsets and interfacial charge-transfer kinetics to ensure long-lived charge carriers that can be delivered at low overpotentials to the appropriate catalytic sites while mitigating parasitic reactions such as photocorrosion. Here we detail the theory-guided design and synthesis of nanowire/quantum dot heterostructures with interfacial electronic structure specifically tailored to promote light-induced charge separation and photocatalytic proton reduction. Topochemical synthesis yields a metastable β-Sn0.23V2O5 compound exhibiting Sn 5s-derived midgap states ideally positioned to extract photogenerated holes from interfaced CdSe quantum dots. The existence of these midgap states near the upper edge of the valence band (VB) has been confirmed, and β-Sn0.23V2O5/CdSe heterostructures have been shown to exhibit a 0 eV midgap state-VB offset, which underpins ultrafast subpicosecond hole transfer. The β-Sn0.23V2O5/CdSe heterostructures are further shown to be viable photocatalytic architectures capable of efficacious hydrogen evolution. The results of this study underscore the criticality of precisely tailoring the electronic structure of semiconductor components to effect rapid charge separation necessary for photocatalysis