Chemical Transformations Research Articles

How the Chemical Properties of Polysaccharides Make It Possible to Design Various Types of Organic–Inorganic Composites for Catalytic Applications

Recently, the use of plant-origin materials has become especially important due to the aggravation of environmental problems and the shortage and high cost of synthetic materials. One of the potential candidates among natural organic compounds is polysaccharides, characterized by a number of advantages over synthetic polymers. In recent years, natural polysaccharides have been used to design composite catalysts for various organic syntheses. This review is devoted to the current state of application of polysaccharides (chitosan, starch, pectin, cellulose, and hydroxyethylcellulose) and composites based on their catalysis. The article is divided into four main sections based on the type of polysaccharide: (1) chitosan-based nanocomposites; (2) pectin-based nanocomposites; (3) cellulose (hydroxyethylcellulose)-based nanocomposites; and (4) starch-based nanocomposites. Each section describes and summarizes recent studies on the preparation and application of polysaccharide-containing composites in various chemical transformations. It is shown that by modifying polysaccharides, polymers with special properties can be obtained, thus expanding the range of biocomposites for catalytic applications.

Positive and Negative Impacts of Interfacial Hydrogen Bonds on Photocatalytic Hydrogen Evolution.

Understanding the behavior of water molecules at solid-liquid interfaces is crucial for various applications such as photocatalytic water splitting, a key technology for sustainable fuel production and chemical transformations. Despite extensive studies conducted in the past, the impact of the microscopic structure of interfacial water molecules on photocatalytic reactivity has not been directly examined. In this study, using real-time mass spectrometry and Fourier-transform infrared spectroscopy, we demonstrated the crucial role of hydrogen bond (H-bond) networks on the photocatalytic hydrogen evolution in thickness-controlled water adsorption layers on various TiO2 photocatalysts. Under controlled water vapor environments with relative humidity (RH) below 70%, we observed a monotonic increase in the H2 formation rate with increasing RH, indicating that reactive water molecules were present not only in the first adsorbed layer but also in several overlying layers. In contrast, at RH > 70%, when more than three water layers covered the catalyst surface, the H2 formation rate turned to decrease dramatically because of the structural rearrangement and hardening of the interfacial H-bond network induced during further water adsorption. This unique many-body effect of interfacial water was consistently observed for various TiO2 particles with different crystalline structures, including brookite, anatase, and a mixture of anatase and rutile. Our results demonstrated that depositing several water layers in a water vapor environment with RH ∼ 70% is optimal for photocatalytic hydrogen evolution rather than liquid-phase reaction conditions in aqueous solutions. This study provides molecular-level insights into designing interfacial water conditions to enhance photocatalytic performance.

Visualization of the Charging of Water Droplets Sprayed into Air.

Water droplets are spraying into air using air as a nebulizing gas, and the droplets pass between two parallel metal plates with opposite charges. A high-speed camera records droplet trajectories in the uniform electric field, providing visual evidence for the Lenard effect, that is, smaller droplets are negatively charged whereas larger droplets are positively charged. By analyzing the velocities of the droplets between the metal plates, the charges on the droplets can be estimated. Some key observations include: (1) localized electric fields with intensities on the order of 109 V/m are generated, and charges are expected to jump (micro-lightening) between a positively charged larger droplet and the negatively charged smaller droplet as they separate; (2) the strength of the electric field is sufficiently powerful to ionize gases surrounding the droplets; and (3) observations in an open-air mass spectrometer reveal the presence of ions such as N2+, O2+, NO+, and NO2+. These findings provide new insight into the origins of some atmospheric ions and have implications for understanding ionization processes in the atmosphere and chemical transformations in water droplets, advancing knowledge in the field of aerosol science and water microdroplet chemistry.

Decreasing the Bond Order between Vanadium and Oxo Ligand to Form 3d Schrock Carbynes.

Preserving vanadium in a high oxidation state during chemical transformations can be challenging due to the oxidizing nature of V(+5) species. Oxo and similar isoelectronic ligands have been utilized to stabilize V(+5) by extensive π-donation. However, decreasing the bond order between V and the oxo ligand often results in a reduction of the metal center. Herein, we report a unique transformation involving anionic V(+5) alkylidene that converts a V(+5) oxo complex to a V(+5) alkylidyne in three steps without altering the oxidation state of the metal center. This method has been used to obtain rare 3d Schrock carbynes, which provide easy and scalable access to V(+5) alkylidynes.

Magnesium Nanoparticles for Surface-Enhanced Raman Scattering and Plasmon-Driven Catalysis.

Nanostructures of some metals can sustain localized surface plasmon resonances, collective oscillations of free electrons excited by incident light. This effect results in wavelength-dependent absorption and scattering, enhancement of the incident electric field at the metal surface, and generation of hot carriers as a decay product. The enhanced electric field can be utilized to amplify the spectroscopic signal in surface-enhanced Raman scattering (SERS), while hot carriers can be exploited for catalytic applications. In recent years, cheaper and more earth abundant alternatives to traditional plasmonic Au and Ag have gained growing attention. Here, we demonstrate the ability of plasmonic Mg nanoparticles to enhance Raman scattering and drive chemical transformations upon laser irradiation. The plasmonic properties of Mg nanoparticles are characterized at the bulk and single particle level by optical spectroscopy and scanning transmission electron microscopy coupled with electron energy-loss spectroscopy and supported by numerical simulations. SERS enhancement factors of ∼102 at 532 and 633 nm are obtained using 4-mercaptobenzoic acid and 4-nitrobenzenethiol. Furthermore, the reductive coupling of 4-nitrobenzenethiol to 4,4'-dimercaptoazobenzene is observed on the surface of Mg nanoparticles under 532 nm excitation in the absence of reducing agents, indicating a plasmon-driven catalytic process. Once decorated with Pd, Mg nanostructures display an enhancement factor of 103 along with an increase in the rate of catalytic coupling. The results of this study demonstrate the successful application of plasmonic Mg nanoparticles in sensing and plasmon-enhanced catalysis.

From transformations to the notion of time

In this paper I expose an ontological-existential interpretation of time via its unveiling and analysis in an example of scientific measurement in a chemical transformation. I begin with the search for time in the transformation, and little by little I explain its characteristics and structures. I finally interpret the time involved in the measurement and the usual concept of linear time by means of the Heidegger's concept of temporality (originary time). The paper is an attempt to explain Heidegger's existential ontology to non-specialist thinkers interested in understanding the subject of time from approaches different from those of their field, as may be the case of many contemporary scientists. For this reason, it develops the ideas step by step and in an expository way, but gradually entering the precise and rigorous Heideggerian terminology necessary for the temporal analysis. Finally, it should be noted that this work contains novel interpretations of several of the ideas and expressions of Heidegger's thought.

Parameterization of Dust Emissions from Heaps and Excavations Based on Measurement Results and Mathematical Modelling

Assessment of the concentrations of dust pollution resulting from both measurements at reference stations and those determined using mathematical modelling requires accurate identification of the sources of emission. Although the concentration of dust results from several complex transport processes, as well as chemical and microphysical transformations of aerosols, sources of emissions may have a significant impact on the local level of pollution. This pilot study aimed to use measurements of the concentrations of dust (with the specification of the PM10 and PM2.5 fractions) made over a heap/excavation and its surroundings using an airship equipped with equipment for testing the optical and microphysical properties of atmospheric aerosols, and a ground station located at the facility. On the basis of the measurements, the function of the source of emissions of dust was estimated. According to our study, the yearly emission of dust varies between 42 470 and 886 289 kg for PM10, and between 42 470 and 803 893 for PM2.5 (minimum and maximum values). A model of local air quality was also used, which allowed us to verify the parameterization of emissions of dust pollutants for the PM10 and PM2.5 fractions from heaps and excavations based on the modelling results.

Regiochemical Analysis of the ProTide Activation Mechanism.

ProTides are nucleotide analogues used for the treatment of specific viral infections. These compounds consist of a masked nucleotide that undergoes in vivo enzymatic and spontaneous chemical transformations to generate a free mononucleotide that is ultimately transformed to the pharmaceutically active triphosphorylated drug. The three FDA approved ProTides are composed of a phosphoramidate (P-N) core coupled with a nucleoside analogue, phenol, and an l-alanyl carboxylate ester. The previously proposed mechanism of activation postulates the existence of an unstable 5-membered mixed anhydride cyclic intermediate formed from the direct attack of the carboxylate group of the l-alanyl moiety with expulsion of phenol. The mixed anhydride cyclic intermediate is further postulated to undergo spontaneous hydrolysis to form a linear l-alanyl phosphoramidate product. In the proposed mechanism of activation, the 5-membered mixed anhydride intermediate has been detected previously using mass spectrometry, but the specific site of nucleophilic attack by water (P-O versus C-O) has not been determined. To further interrogate the mechanism for hydrolysis of the putative 5-membered cyclic intermediate formed during ProTide activation, the reaction was conducted in 18O-labeled water using a ProTide analogue that could be activated by carboxypeptidase Y. Mass spectrometry and 31P NMR spectroscopy were used to demonstrate that the hydrolysis of the mixed anhydride 5-membered intermediate occurs with exclusive attack at the phosphorus center.

Enhancing sorption kinetics by oriented and single crystalline array-structured ZSM-5 film on monoliths

To enhance the reaction kinetics without sacrificing activity in porous materials, one potential solution is to utilize the anisotropic distribution of pores and channels besides enriching active centers at the reactive surfaces. Herein, by designing a unique distribution of oriented pores and single crystalline array structures in the presence of abundant acid sites as demonstrated in the ZSM-5 nanorod arrays grown on monoliths, both enhanced dynamics and improved capacity are exhibited simultaneously in propene capture at low temperature within a short duration. Meanwhile, the ZSM-5 array also helps mitigate the long-chain HCs and coking formation due to the enhanced diffusion of reactants in and reaction products out of the array structures. Further integrating the ZSM-5 array with Co3O4 nanoarray enables comprehensive propene removal throughout a wider temperature range. The array structured film design could offer energy-efficient solutions to overcome both sorption and reaction kinetic restrictions in various solid porous materials for various energy and chemical transformation applications.

Synergy and site dependent kinetics of photo-thermal catalysis over Pt/TiO2 for methanol decomposition

Photo-thermal catalysis which interplay the heat and light-induced effects have drawn broad attention owing to their synergistic effect to extend the capability of chemical transformation. Here, the effect of heat and/or light on methanol decomposition has been clarified. On Pt/TiO2, light irradiation activates the TiO2 and enhance the absorption and the oxidation of intermediates. The main intermediate under PTC condition is formaldehyde, which is the same to TC condition rather than methyl formate under PC condition. Differences CO absorption site correlates with the key intermediates under PC and TC/PTC conditions. Light and heat display their strengths in a synergistic manner, optimizing the activity to promote efficient catalytic processes which is verified to be photo-assisted thermal catalysis. This work offers detailed mechanistic understanding of the surface species and paves the way for an educated microkinetic modeling approach under photo and/or thermal condition over oxide-supported metal catalysts.

In-situ chemical state transition of Ni nano-metal catalytic site promotes the reaction kinetics of lithium-sulfur battery

Researchers have extensively explored the implementation of metal-based catalysts to address the slow conversion kinetics of lithium polysulfides (LiPSs) in lithium-sulfur (Li-S) batteries. However, the elucidation of foundational aspects, such as the in-situ transformation processes of monometallic catalysts within the Li-S battery reaction milieu, as well as the chemical states of resultant catalytic active centers, remains elusive. In this study, a flexible material (CBC/Ni) was prepared, consisting of a carbonized bacterial cellulose framework uniformly loaded with nickel nanoparticles, serving as a sulfur host. Through in-situ XRD and in-situ Raman studies, it was demonstrated that the nanoscale Ni catalyst in the S@CBC/Ni electrode undergoes an interaction with LiPSs during the operation of Li-S batteries, transforming into the chemical state of NiS2 and subsequently acting as a new active center to promote the conversion of LiPSs in the subsequent cycling process. Due to these advantageous characteristics, the S@CBC/Ni cathode delivers a high-rate capacity of 798.7 mAh/g at 2C, with an average capacity decay rate of only 0.064% over 500 cycles. This work provides a theoretical reference for the in-situ chemical transformation and functionality of nanoscale metal catalysts in the Li-S system.

Precision spectroscopy of non-thermal molecular plasmas using mid-infrared optical frequency comb Fourier transform spectroscopy

Non-thermal molecular plasmas play a crucial role in numerous industrial processes and hold significant potential for driving essential chemical transformations. Accurate information about the molecular composition of the plasmas and the distribution of populations among quantum states is essential for understanding and optimizing plasma processes. Here, we apply a mid-infrared frequency comb-based Fourier transform spectrometer to measure high-resolution spectra of plasmas containing hydrogen, nitrogen, and a carbon source in the 2800–3400 cm–1 range. The spectrally broadband and high-resolution capabilities of this technique enable quantum-state-resolved spectroscopy of multiple plasma-generated species simultaneously, including CH4, C2H2, C2H6, NH3, and HCN, providing detailed information beyond the limitations of current methods. Using a line-by-line fitting approach, we analyzed 548 resolved transitions across five vibrational bands of plasma-generated HCN. The results indicate a significant non-thermal distribution of the populations among the quantum states, with distinct temperatures observed for lower and higher rotational quantum numbers, with a temperature difference of about 62 K. Broadband state-resolved-spectroscopy via comb-based methods provides unprecedented fundamental insights into the non-thermal nature of molecular plasmas—a detailed picture that has never been accomplished before for such complex non-thermal environment.

High Mobility Transistors and Flexible Optical Synapses Enabled by Wafer-Scale Chemical Transformation of Pt-Based 2D Layers.

Electronic devices employing two-dimensional (2D) van der Waals (vdW) transition-metal dichalcogenide (TMD) layers as semiconducting channels often exhibit limited performance (e.g., low carrier mobility), in part, due to their high contact resistances caused by interfacing non-vdW three-dimensional (3D) metal electrodes. Herein, we report that this intrinsic contact issue can be efficiently mitigated by forming the 2D/2D in-plane junctions of 2D semiconductor channels seamlessly interfaced with 2D metal electrodes. For this, we demonstrated the selectively patterned conversion of semiconducting 2D PtSe2 (channels) to metallic 2D PtTe2 (electrodes) layers by employing a wafer-scale low-temperature chemical vapor deposition (CVD) process. We investigated a variety of field-effect transistors (FETs) employing wafer-scale CVD-2D PtSe2/2D PtTe2 heterolayers and identified that silicon dioxide (SiO2) top-gated FETs exhibited an extremely high hole mobility of ∼120 cm2 V-1 s-1 at room temperature, significantly surpassing performances with previous wafer-scale 2D PtSe2-based FETs. The low-temperature nature of the CVD method further allowed for the direct fabrication of wafer-scale arrays of 2D PtSe2/2D PtTe2 heterolayers on polyamide (PI) substrates, which intrinsically displayed optical pulse-induced artificial synaptic behaviors. This study is believed to vastly broaden the applicability of 2D TMD layers for next-generation, high-performance electronic devices with unconventional functionalities.

Chemical Transformations of Benzyl Alcohol Caused by Atomic Chlorine.

Atomic chlorine present in the polluted troposphere can form potentially carcinogenic compounds as a result of a reaction with a natural product. This paper examines the stability of benzyl alcohol-a natural product commonly found in cosmetics-in interaction with atomic chlorine, which is becoming ever more present in the Earth's atmosphere as a result of its pollution. Research shows that atomic chlorine generated in the gas phase easily penetrates the liquid phase of benzyl alcohol, resulting in the formation of hydrochloric acid. The resulting HCl initiates further transformations of benzyl alcohol. Our study presents the amounts of the reaction products. The quantitative analysis was made using the GC method, and all the products were identified using the GC-MS method. The products include dichloromethyl benzene, 2-chlorobenzyl alcohol, and 3-chlorobenzyl alcohol, which are harmful, but are formed in very small amounts. The harmful substance occurring in a much higher amount is benzyl chloride-that is a product of acidification of benzyl alcohol by HCl.

Chemical upcycling of polyolefins into liquid refinery feedstock from the circularity and chemical engineering aspects

Three quarters of all plastics produced each year are discarded to landfill after a single use without proper waste management practices, causing a global environmental crisis: waste plastics suffocating our world at enormously large volumes. Discarding plastics into landfill, inefficiently processing them to lower value materials, or incinerating them cause an irreversible loss of the stored energy in plastics. These plastics, however, represent a tremendous resource for the production of chemicals and can be upcycled into high-quality value-added refinery feedstock that could be used to produce virgin polyolefins. In this article, we review pyrolysis and hydrogenolysis based chemical transformations to convert waste polyolefins into liquid hydrocarbons with a special emphasis on life cycle assessment (LCA), reactor technologies, and integration to existing refineries. Several patented technologies are described in detail to shed a light on engineering aspects of the chemical recycling. Liquid products obtained from chemical recycling are examined from the circularity point of view. Feedstock and stream locations in existing refineries and around steam crackers are recommended to feed and/or blend the products obtained from chemical recycling of polyolefins. Challenges, perspectives, and emerging areas of research and engineering are mentioned.

How the secrets behind photocurrents are revealed in Ag-TiO2 heterostructures-based plasmonic photoelectrochemical systems: A collaborative approach of EC-SERS and photoelectrochemical methods

Plasmon-mediated chemical reactions (PMCR) have garnered growing interest as a promising concept for photocatalysis. However, in electrochemical systems at solid–liquid interfaces, the photo-induced charge transfer on the surface of metal–semiconductor heterostructures involves complex processes and mechanisms, which are still poorly understood. We explore the plasmon-mediated carrier transfer mechanism and the synergistic effect of light and electric fields on Ag-TiO2 heterostructures, through a combination of electrochemical surface-enhanced Raman spectroscopy and photoelectrochemical methods, with para-aminothiophenol (PATP) serving as a probe molecule. The results show that photocurrent responses are dependent on not only excitation wavelengths and applied potentials, but also the irreversibility of redox. The relationship between photocurrent responses and the chemical transformation between PATP and 4,4′-dimercaptoazobenzene is established, reflecting the photo-induced charge transfer of the heterostructures. The collaboration of spectroscopic and photoelectrochemical methods provide valuable insights into the chemical transformation and kinetic information of adsorbed molecules on the heterostructure during PMCR, offering opportunities for modulating of photocatalytic activities of hot carriers.

Efficient Process Development of Abiraterone Acetate by Employing Design of Experiments.

This article describes an efficient process for the synthesis of abiraterone acetate by employing Quality by Design (QbD) principles and statistical design of experiments (DoE). It focuses on the identification of critical quality attributes (CQAs), the relationship between CQAs and material attributes (MAs), and critical process parameters (CPPs) for the synthesis of hydrazone, vinyl iodide intermediates, and final product. Risk assessment is employed to identify the probable critical factors involved in each chemical transformation. The design of experiments approach aided in controlling the formation of critical impurities in all three reactions, namely, deacylated impurity in the hydrazone intermediate, 17-methyl impurity in the vinyl iodide intermediate, and hydroxy and diene impurities in the final API. The process was developed such that we achieved 95, 85, and 82% selectivity and 99, 96, and 99% purity in hydrazone, vinyl iodide intermediate, and final API, respectively. This reflects improved throughput from 25 to 57% as a result of the subtle interplay of critical process parameters identified by DoE studies.

Direct Synthesis of α-Ketothioamide Derivatives through a One-Pot Reaction of Sulfur Ylides, Nitrosobenzenes, and Thioacetic Acid.

A one-pot approach has been developed for the synthesis of α-ketothioamide derivatives from sulfur ylides, nitrosobenzenes, and thioacetic acid. This protocol is carried out under mild reaction conditions in generally moderate to excellent yields without any precious catalysts, affording the derivatives with structural diversity. Additionally, a possible mechanism for this chemical transformation is proposed.

Oxygenation of Earth's atmosphere induced metabolic and ecologic transformations recorded in the Lomagundi-Jatuli carbon isotopic excursion.

The oxygenation of Earth's atmosphere represents the quintessential transformation of a planetary surface by microbial processes. In turn, atmospheric oxygenation transformed metabolic evolution; molecular clock models indicate the diversification and ecological expansion of respiratory metabolisms in the several hundred million years following atmospheric oxygenation. Across this same interval, the geological record preserves 13C enrichment in some carbonate rocks, called the Lomagundi-Jatuli excursion (LJE). By combining data from geologic and genomic records, a self-consistent metabolic evolution model emerges for the LJE. First, fermentation and methanogenesis were major processes remineralizing organic carbon before atmospheric oxygenation. Once an ozone layer formed, shallow water and exposed environments were shielded from UVB/C radiation, allowing the expansion of cyanobacterial primary productivity. High primary productivity and methanogenesis led to preferential removal of 12C into organic carbon and CH4. Extreme and variable 13C enrichments in carbonates were caused by 13C-depleted CH4 loss to the atmosphere. Through time, aerobic respiration diversified and became ecologically widespread, as did other new metabolisms. Respiration displaced fermentation and methanogenesis as the dominant organic matter remineralization processes. As CH4 loss slowed, dissolved inorganic carbon in shallow environments was no longer highly 13C enriched. Thus, the loss of extreme 13C enrichments in carbonates marks the establishment of a new microbial mat ecosystem structure, one dominated by respiratory processes distributed along steep redox gradients. These gradients allowed the exchange of metabolic by-products among metabolically diverse organisms, providing novel metabolic opportunities. Thus, the microbially induced oxygenation of Earth's atmosphere led to the transformation of microbial ecosystems, an archetypal example of planetary microbiology.IMPORTANCEThe oxygenation of Earth's atmosphere represents the most extensive known chemical transformation of a planetary surface by microbial processes. In turn, atmospheric oxygenation transformed metabolic evolution by providing oxidants independent of the sites of photosynthesis. Thus, the evolutionary changes during this interval and their effects on planetary-scale biogeochemical cycles are fundamental to our understanding of the interdependencies among genomes, organisms, ecosystems, elemental cycles, and Earth's surface chemistry through time.

Ozonolysis of Terpene Flavor Additives in Vaping Emissions: Elevated Production of Reactive Oxygen Species and Oxidative Stress.

The production of e-cigarette aerosols through vaping processes is known to cause the formation of various free radicals and reactive oxygen species (ROS). Despite the well-known oxidative potential and cytotoxicity of fresh vaping emissions, the effects of chemical aging on exhaled vaping aerosols by indoor atmospheric oxidants are yet to be elucidated. Terpenes are commonly found in e-liquids as flavor additives. In the presence of indoor ozone (O3), e-cigarette aerosols that contain terpene flavorings can undergo chemical transformations, further producing ROS and reactive carbonyl species. Here, we simulated the aging process of the e-cigarette emissions in a 2 m3 FEP film chamber with 100 ppbv of O3 exposure for an hour. The aged vaping aerosols, along with fresh aerosols, were collected to detect the presence of ROS. The aged particles exhibited 2- to 11-fold greater oxidative potential, and further analysis showed that these particles formed a greater number of radicals in aqueous conditions. The aging process induced the formation of various alkyl hydroperoxides (ROOH), and through iodometric quantification, we saw that our aged vaping particles contained significantly greater amounts of these hydroperoxides than their fresh counterparts. Bronchial epithelial cells exposed to aged vaping aerosols exhibited an upregulation of the oxidative stress genes, HMOX-1 and GSTP1, indicating the potential for inhalation toxicity. This work highlights the indirect danger of vaping in environments with high ground-level O3, which can chemically transform e-cigarette aerosols into new particles that can induce greater oxidative damage than fresh e-cigarette aerosols. Given that the toxicological characteristics of e-cigarettes are mainly associated with the inhalation of fresh aerosols in current studies, our work may provide a perspective that characterizes vaping exposure under secondhand or thirdhand conditions as a significant health risk.