Electro-inductive effect: Electrodes as functional groups with tunable electronic properties

© 2020, The Authors. In place of functional groups that impose different inductive effects, we immobilize molecules carrying thiol groups on a gold electrode. By applying different voltages, the properties of the immobilized molecules can be tuned. The base-catalyzed saponification of benzoic esters is fully inhibited by applying a mildly negative voltage of -0.25 volt versus open circuit potential. Furthermore, the rate of a Suzuki-Miyaura cross-coupling reaction can be changed by applying a voltage when the arylhalide substrate is immobilized on a gold electrode. Finally, a two-step carboxylic acid amidation is shown to benefit from a switch in applied voltage between addition of a carbodiimide coupling reagent and introduction of the amine11sciescopu

b₂ Peaks in SERS Spectra of 4‑Aminobenzenethiol: A Photochemical Artifact or a Real Chemical Enhancement?

Strong b₂ peaks (1142, 1391, 1438, and 1583 cm^–1) in the SERS spectra of 4-aminobenzenethiol (ABT) have been regarded by many as a textbook example of chemically enhanced SERS signals. However, this interpretation is in serious doubt after the recent claim that they arise from 4,4′-dimercaptoazobenzenes (DMAB) photogenerated during the acquisition of SERS, not the genuine chemically enhanced signals of ABT. Subsequent attempts to prove or disprove this claim have failed to provide any decisive verdict. Here we present spectroscopic and mass spectrometric evidence that further support the photogeneration of DMABs from ABTs on an Ag surface. Furthermore, we show that the amount of the DMAB is sufficient to explain the b₂ intensities of ABT

Label-Free Calcium Imaging in Ischemic Retinal Tissue by TOF-SIMS

The distribution and movement of elemental ions in biologic tissues is critical for many cellular processes. In contrast to chemical techniques for imaging the intracellular distribution of ions, however, techniques for imaging the distribution of ions across tissues are not well developed. We used time-of-flight secondary ion mass spectrometry (TOF-SIMS) to obtain nonlabeled high-resolution analytic images of ion distribution in ischemic retinal tissues. Marked changes in Ca2+ distribution, compared with other fundamental ions, such as Na+, K+, and Mg2+, were detected during the progression of ischemia. Furthermore, the Ca2+ redistribution pattern correlated closely with TUNEL-positive (positive for terminal deoxynucleotidyl transferase-mediated 2′-deoxyuridine 5′-triphosphate nick end-labeling) cell death in ischemic retinas. After treatment with a calcium chelator, Ca2+ ion redistribution was delayed, resulting in a decrease in TUNEL-positive cells. These results indicate that ischemia-induced Ca2+ redistribution within retinal tissues is associated with the order of apoptotic cell death, which possibly explains the different susceptibility of various types of retinal cells to ischemia. Thus, the TOF-SIMS technique provides a tool for the study of intercellular communication by Ca2+ ion movement

Electrochemical Release of Amine Molecules from Carbamate-Based, Electroactive Self-Assembled Monolayers

In this paper, carbamate-based self-assembled monolayers (SAMs) of alkanethiolates on gold were suggested as a versatile platform for release of amine-bearing molecules in response to the electrical signal. The designed SAMs underwent the electrochemical oxidation on the gold surface with simultaneous release of the amine molecules. The synthesis of the thiol compounds was achieved by coupling isocyanate-containing compounds with hydroquinone. The electroactive thiol was mixed with 11-mercaptoundecanol [HS(CH₂)₁₁OH] to form a mixed monolayer, and cyclic votammetry was used for the characterization of the release behaviors. The mixed SAMs showed a first oxidation peak at +540 mV (versus Ag/AgCl reference electrode), indicating the irreversible conversion from carbamate to hydroquinone groups with simultaneous release of the amine molecules. The analysis of ToF-SIMS further indicated that the electrochemical reaction on the gold surface successfully released amine molecules

Monitoring Lipid Alterations in Drosophila Heads in an Amyotrophic Lateral Sclerosis Model with Time-of-Flight Secondary Ion Mass Spectrometry

Lipid alterations in the brain are well-documented in disease and aging, but our understanding of their pathogenic implications remains incomplete. Recent technological advances in assessing lipid profiles have enabled us to intricately examine the spatiotemporal variations in lipid compositions within the complex brain characterized by diverse cell types and intricate neural networks. In this study, we coupled time-of-flight secondary ion mass spectrometry (ToF-SIMS) to an amyotrophic lateral sclerosis (ALS) Drosophila model, for the first time, to elucidate changes in the lipid landscape and investigate their potential role in the disease process, serving as a methodological and analytical complement to our prior approach that utilized matrix-assisted laser desorption/ionization mass spectrometry. The expansion of G4C2 repeats in the C9orf72 gene is the most prevalent genetic factor in ALS. Our findings indicate that expressing these repeats in fly brains elevates the levels of fatty acids, diacylglycerols, and ceramides during the early stages (day 5) of disease progression, preceding motor dysfunction. Using RNAi-based genetic screening targeting lipid regulators, we found that reducing fatty acid transport protein 1 (FATP1) and Acyl-CoA-binding protein (ACBP) alleviates the retinal degeneration caused by G4C2 repeat expression and also markedly restores the G4C2-dependent alterations in lipid profiles. Significantly, the expression of FATP1 and ACBP is upregulated in G4C2-expressing flies, suggesting their contribution to lipid dysregulation. Collectively, our novel use of ToF-SIMS with the ALS Drosophila model, alongside methodological and analytical improvements, successfully identifies crucial lipids and related genetic factors in ALS pathogenesis.TRU

Sulfuric Acid Treated g-CN as a Precursor to Generate High-Efficient g-CN for Hydrogen Evolution from Water under Visible Light Irradiation

Modifying the physical, chemical structures of graphitic carbon nitride (g-CN) to improve its optoelectronic properties is the most efficient way to meet a high photoactivity for clean and sustainable energy production. Herein, a higher monomeric precursor for synthesizing improved micro-and electronic structure possessing g-CN was prepared by high-concentrated sulfuric acid (SA) treatment of bulk type g-CN (BCN). Several structural analyses show that after the SA treatment of BCN, the polymeric melon-based structure is torn down to cyameluric or cyanuric acid-based material. After re-polycondensation of this material as a precursor, the resulting g-CN has more condensed microstructure, carbon and oxygen contents than BCN, indicating that C, O co-doping by corrosive acid of SA. This g-CN shows a much better visible light absorption and diminished radiative charge recombination by the charge localization effect induced by heteroatoms. As a result, this condensed C, O co-doped g-CN shows the enhanced photocatalytic hydrogen evolution rate of 4.57 µmol/h from water under the visible light (>420 nm) by almost two times higher than that of BCN (2.37 µmol/h). This study highlights the enhanced photocatalytic water splitting performance as well as the provision of the higher monomeric precursor for improved g-CN