Volume 93, Issue 2

Site-specific protein conjugation is a critical step in the generation of unique protein analogs for a range of basic research and therapeutic developments. Protein transformations must target a precise residue in the presence of a plethora of functional groups to obtain a well-characterized homogeneous product. Competing reactive residues on natural proteins render rapid and selective conjugation a challenging task. Organometallic reagents have recently emerged as a powerful strategy to achieve site-specific labeling of a diverse set of biopolymers, due to advances in water-soluble ligand design, high reaction rate, and selectivity. The thiophilic nature of various transition metals, especially soft metals, makes cysteine an ideal target for these reagents. The distinctive reactivity and selectivity of organometallic-based reactions, along with the unique reactivity and abundancy of cysteine within the human proteome, provide a powerful platform to modify native proteins in aqueous media. These reactions often provide the modified proteins with a stable linkage made from irreversible cross-coupling steps. Additionally, transition metal reagents have recently been applied for the decaging of cysteine residues in the context of chemical protein synthesis. Orthogonal cysteine protecting groups and functional tags are often necessary for the synthesis of challenging proteins, and organometallic reagents are powerful tools for selective, rapid, and water-compatible removal of those moieties. This review examines transition metal-based reactions of cysteine residues for the synthesis and modification of natural peptides and proteins.

Nanomaterials with enzyme-like activity, generally referred to as ‘nanozymes’, find myriad potential in various biomedical fields. More importantly, the nanoparticles that can functionally mimic the activity of cellular antioxidant enzymes attract tremendous interest owing to their possible therapeutic candidature in oxidative stress-mediated disorders. Oxidative stress culminating due to excess reactive oxygen species (ROS) level and dysregulated cellular antioxidant machinery is implicated in the development and progression of various pathophysiological disorders such as cancer, diabetes, cardiovascular and neurodegenerative diseases. Moreover, the optimum essentiality of ROS due to its pivotal role in cell signaling evokes the requirement of novel artificial antioxidant enzymes that can circumvent the detrimental effects of enhanced ROS levels without perturbing the basal redox status of cells. In recent years, the fast emanating artificial enzymes, i.e. nanozymes with antioxidant enzyme-like activity, has made tremendous progress with their broad applications in therapeutics, diagnostic medicine, bio-sensing, and immunoassay. Among various antioxidant nanoparticles reported till-date, the metal oxide nanozymes have emerged as the most efficient and successful candidates in mimicking the activity of first-line defense antioxidant enzymes, i.e. superoxide dismutase, catalase, and glutathione peroxidase. This review intends to exclusively highlight the development of representative metal oxide-based antioxidant nanozymes capable of maintaining the cellular redox homeostasis and their potential therapeutic significance.

This work describes select narratives pertaining to undergraduate teaching and mentorship at UCLA Chemistry and Biochemistry by Alex Spokoyny and his junior colleagues. Specifically, we discuss how individual undergraduate researchers contributed and jump-started multiple research themes since the conception of our research laboratory. This work also describes several recent innovations in the inorganic and general chemistry courses taught by Spokoyny at UCLA with a focus of nurturing appreciation for research and creative process in sciences including the use of social media platforms.

Photogenerated charge carriers in organic photovoltaics (OPVs) suffer relaxation and recombination losses. However, extracting these carriers at higher energy (‘Hot-carriers’) has been found to be effective to overcome such loss pathways and improve efficiency of OPVs. Excess energy and long delocalization length promotes hot-carrier escape from Coulombic attraction and dissociation into free charges. Here, I have reviewed the ways to generate hot-carriers and their extraction in organic backbones. In-depth understanding of their energetics and dynamics will help designing hot-carrier photovoltaics.

Oxidative desulfurization is a promising way to produce, under mild conditions, clean ecological fuels with ultra-low sulfur content. Herein, we present for the first time heterogeneous catalysts based on natural aluminosilicate nanotubes (halloysite) loaded with transition metal oxides for oxidative sulfur removal using hydrogen peroxide as environmentally safe oxidant. The halloysite nanotubes (HNTs) provide acid sites for C–S bond scission, while the Mo and W oxides act as hydrogen peroxide activators. The structure and acidity of both the clay support and catalysts were investigated by low-temperature nitrogen adsorption/desorption, Fourier-transform infrared spectroscopy, X-ray fluorescence analysis, and transmission electron microscopy techniques. These clay-based catalysts revealed the high activity in the oxidation of various classes of sulfur-containing compounds (sulfides, heteroatomic sulfur compounds) under mild reaction conditions. The conversion of various substrates decreases in the following trend: MeSPh > Bn2S > DBT > 4-MeDBT > BT, which deals with substrate electron density and steric hindrance. The influence of the temperature, oxidant to sulfur molar ratio, and reaction time on catalytic behavior was evaluated for Mo- and W-containing systems with various metal content. The complete oxidation of the most intractable dibenzothiophene to the corresponding sulfone was achieved at 80 °C and H 2 O 2 :S = 6:1 (molar) for 2 h both for Mo- and W-containing systems. These transition metal oxides HNTs supported catalysts are stable for 10 cycles of dibenzothiophene oxidation, which makes them promising systems for clean fuel production.

According to the 1994 IUBMB-IUPAC Joint Commission on Biochemical Nomenclature (JCBN) on chemical and biochemical reactions, two categories of thermodynamics, based on different concepts and different formalisms, are established: (i) chemical thermodynamics, which employ conventional thermodynamic potentials to deal with chemical reactions [1], [2], [3]; and (ii) biochemical thermodynamics, which employ transformed thermodynamic quantities to deal with biochemical reactions based on the formalism proposed by Alberty [4], [5], [6], [7]. We showed that the two worlds of chemical and biochemical thermodynamics, which so far have been treated separately, can be reunified within the same thermodynamic framework. The thermodynamics of chemical reactions, in which all species are explicitly considered with their atoms and charge balanced, are compared with the transformed thermodynamics generally used to treat biochemical reactions where atoms and charges are not balanced. The transformed thermodynamic quantities suggested by Alberty are obtained by a mathematical transformation of the usual thermodynamic quantities. The present analysis demonstrates that the transformed values for Δ r G ′ 0 and Δ r H ′ 0 can be obtained directly, without performing any transformation, by simply writing the chemical reactions with all the pseudoisomers explicitly included and the elements and charges balanced. The appropriate procedures for computing the stoichiometric coefficients for the pseudoisomers are fully explained by means of an example calculation for the biochemical ATP hydrolysis reaction. It is concluded that the analysis reunifies the “two separate worlds” of conventional thermodynamics and transformed thermodynamics.

Scientific projects frequently involve measurements of thermophysical, thermochemical, and other related properties of chemical compounds and materials. These measured property data have significant potential value for the scientific community, but incomplete and inaccurate reporting often hampers their utilization. The present IUPAC Technical Report summarizes the needs of chemical engineers and researchers as consumers of these data and shows how publishing practices can improve information transfer. In the Report, general principles of Good Reporting Practice are developed together with examples illustrating typical cases of reporting issues. Adoption of these principles will improve the quality, reproducibility, and usefulness of experimental data, bring a better level of consistency to results, and increase the efficiency and impact of research. Closely related to Good Reporting Practice , basic elements of Good Research Practice are also introduced with a goal to reduce the number of ambiguities and unresolved problems within the thermophysical property data domain.