Chemistry Of Products Research Articles

Advances in Humidity Nanosensors and Their Application: Review.

As the technology revolution and industrialization have flourished in the last few decades, the development of humidity nanosensors has become more important for the detection and control of humidity in the industry production line, food preservation, chemistry, agriculture and environmental monitoring. The new nanostructured materials and fabrication in nanosensors are linked to better sensor performance, especially for superior humidity sensing, following the intensive research into the design and synthesis of nanomaterials in the last few years. Various nanomaterials, such as ceramics, polymers, semiconductor and sulfide, carbon-based, triboelectrical nanogenerator (TENG), and MXene, have been studied for their potential ability to sense humidity with structures of nanowires, nanotubes, nanopores, and monolayers. These nanosensors have been synthesized via a wide range of processes, including solution synthesis, anodization, physical vapor deposition (PVD), or chemical vapor deposition (CVD). The sensing mechanism, process improvement and nanostructure modulation of different types of materials are mostly inexhaustible, but they are all inseparable from the goals of the effective response, high sensitivity and low response-recovery time of humidity sensors. In this review, we focus on the sensing mechanism of direct and indirect sensing, various fabrication methods, nanomaterial geometry and recent advances in humidity nanosensors. Various types of capacitive, resistive and optical humidity nanosensors are introduced, alongside illustration of the properties and nanostructures of various materials. The similarities and differences of the humidity-sensitive mechanisms of different types of materials are summarized. Applications such as IoT, and the environmental and human-body monitoring of nanosensors are the development trends for futures advancements.

Sources of anthropogenic nutrients and their implications on nutrient chemistry and ecological conditions of Ria Formosa lagoon, Portugal

Shallow coastal waters receive high anthropogenic nutrients (nitrogen-N and phosphorus-P) from land that can change their nutrient chemistry, algal composition, and food webs with serious effects on marine life, human health, and local livelihoods. Managing anthropogenic nutrient inputs is thus key to ensuring healthy and productive coastal ecosystems. This study conducted a bimonthly sampling for eight months between 2014 and 2015 to determine the influence of agriculture, sewage, and natural nutrient sources on nutrient chemistry, ecological status, and possible implications for aquaculture production in the western side of Ria Formosa lagoon. Ecological Quality Ratios (EQR) were calculated from nutrient ratios (N: P: Si) computed from nutrient concentrations with the Redfield ratio (N: P: Si =16:1:16) used as a reference for ecological status determination. A mean of 3.7, 1.0, and 4.6μmol/L; 6.7, 1.12, and 5.5μmol/L; and 4.6, 0.7, and 2.8μmol/L were recorded for dissolved inorganic nitrogen, phosphorus and silicates concentrations at sewage, agriculture, and natural sites respectively. The site mean EQR values ranged between 0.55 and 0.69. The overall ecological status of the west part of the lagoon was ‘Moderate’, with all the sites grouped under ‘Good’/’Moderate’ and ‘Moderate’/’Poor’ classes based on nutrient ratios. This study demonstrates that the western part of the lagoon’s nutrient chemistry is highly influenced by the nutrient sources with agricultural run-off and sewage discharges associated with nitrates, and ammonia and phosphates respectively. The elevated ammonium and phosphates registered can transform the phytoplankton composition to non-diatomic species and affect the current ecological functions of the lagoon. We recommend further studies, including biological quality elements, to get more comprehensive results on the study area.

Chemistry and Biology of Acyloin Natural Products

AbstractThis review details the isolation, biosynthesis, biological activity, and synthesis of α-hydroxy ketone (acyloin) natural products. The role of these compounds as biosynthetic precursors to complex natural products and synthetic strategies to access the sensitive acyloin moiety and stereochemistry are highlighted.1 Introduction1.1 Xenocyloins1.2 Biological Activity1.3 Biosynthesis1.4 Acyloins as Discoipyrrole Biosynthetic Precursors2 Total Synthesis of Acyloin Natural Products2.1 Kurasoins A and B2.2 Soraphinol A and Circumcin B2.3 4-Hydroxysattabacin and Actinopolymorphol A2.4 Actinopolymorphol B2.5 Sattazolins and Sattabacins2.6 Catalyst Development and Application in Acyloin Synthesis2.7 Xenocyloins3 Conclusion

99mTc-Labelled Low Molecular Weight Inhibitors of Prostate-Specific Membrane Antigen

High morbidity and mortality rates of prostate cancer (PCa) determine the requirement of looking for new methods of its early diagnosis. Methods of nuclear medicine have a special place in addressing this problem as they allow functional, metabolic and other processes imaging in body, which occur during the cancer development. This approach supposes the use of radiopharmaceuticals (RP), which are capable of selective binding to a specific biological target, for example, prostate-specific membrane antigen (PSMA), which is known to be overexpressed in PCa. Current development of new radiotracers for PCa imaging is focused on low molecular weight PSMA inhibitors due to their high specific binding to PSMA and rapid urinary excretion. Technetium-99m remains the appropriate radionuclide for diagnostic studies due to its optimal nuclear properties, ease of production and versatile coordination chemistry. Therefore, single-photon emission computed tomography (SPECT) imaging with 99mTc-PSMA radioligands can be a cost effective alternative to PET with 68Ga- or 18F-labeled RP. The aim of this review is to summarize and analyze currently available data on 99mTc-labeled low molecular weight PSMA inhibitors for metastatic PCa imaging.

Characterization of the degradation products of lignocellulosic biomass by using tandem mass spectrometry experiments, model compounds, and quantum chemical calculations.

Biomass-derived degraded lignin and cellulose serve as possible alternatives to fossil fuels for energy and chemical resources. Fast pyrolysis of lignocellulosic biomass generates bio-oil that needs further refinement. However, as pyrolysis causes massive degradation to lignin and cellulose, this process produces very complex mixtures. The same applies to degradation methods other than fast pyrolysis. The ability to identify the degradation products of lignocellulosic biomass is of great importance to be able to optimize methodologies for the conversion of these mixtures to transportation fuels and valuable chemicals. Studies utilizing tandem mass spectrometry have provided invaluable, molecular-level information regarding the identities of compounds in degraded biomass. This review focuses on the molecular-level characterization of fast pyrolysis and other degradation products of lignin and cellulose via tandem mass spectrometry based on collision-activated dissociation (CAD). Many studies discussed here used model compounds to better understand both the ionization chemistry of the degradation products of lignin and cellulose and their ions' CAD reactions in mass spectrometers to develop methods for the structural characterization of the degradation products of lignocellulosic biomass. Further, model compound studies were also carried out to delineate the mechanisms of the fast pyrolysis reactions of lignocellulosic biomass. The above knowledge was used to assign likely structures to many degradation products of lignocellulosic biomass.

Simulations of Summertime Ozone and PM2.5 Pollution in Fenwei Plain (FWP) Using the WRF-Chem Model

In recent years, ozone and PM2.5 pollution has often occured in the Fenwei Plain due to heavy emission and favorable geographical conditions. In this study, we used the weather research and forecasting/chemistry (WRF-Chem) model to reproduce the complex air pollution of the ozone and PM2.5 in the Fenwei Plain (FWP) from 20 May to 29 May 2015. By comparing the simulation results with the observed data, we found that although in some cities there was a bias between the simulated values and observed data, the model captured the trend of pollutants generally. Moreover, according to the assessment parameters, we validated that the deviations are acceptable. However, according to these parameters, we found that the WRF-Chem performed better on ozone simulation rather than PM2.5. Based on the validation, we further analyzed the pollutant distribution during the contaminated period. Generally speaking, the polluted area is mainly located in the cities of the Shanxi province and Henan province. Moreover, in this time period, pollution mainly occurred on 27 May and 28 May. In addition, due to different formation conditions of ozone and PM2.5 pollution, the distribution characteristics of these two pollutants were also found to be different. Ozone pollution mainly occurred north of FWP due to the prevailing wind and the chemistry of ozone production. As for PM2.5, the pollution occurred at night and the polluted area was located in the FWP. Furthermore, high PM2.5 areas were closed to emission sources in the FWP, showing a high correlation with primary emissions.

Development of Practicum Module for Making Trimyristin Soap Active Ingredients from Nutmeg Seeds (Myristica fragrans Houtt)

Research This aims to develop practicum module for making soap with natural active ingredients to improve students' creative thinking skills. Practicum instructions will be applied to natural science and natural product chemistry practicum courses to provide innovations and appropriate technology for science education master students. The development of practicum instructions is a Research and Development (R & D) development with a define, design, develop, and disseminate (4D) model. The samples of this research were chemistry students and Master of Science Education students. The tests carried out were tests of physical properties (organoleptic, pH, and homogeneity) and antimicrobial tests with varying concentrations of trimyristin. Products in the form of practicum module are validated. The results showed that the validity value of the three validators obtained using the Aiken index was V = 0.84, which indicated that the natural science practicum module: the procedure for making trimyristin soap from nutmeg, was very valid and feasible to use. Meanwhile, practicality can be seen from the responses of students and lecturers, who show a positive response with average practicality of all components of 88% of student responses and 89% of lecturer responses. The results of the physical evaluation of trimyristin solid soap (organoleptic, pH, foam stability, and moisture content) produced from this study showed good results because they met several standards for the quality of solid soap SNI 3532-2016. Based on these data, the materials chemistry practicum module: procedures for making trimyristin soap from nutmeg seeds to support meaningful learning that is developed is very valid and very practical to use in the learning process

Pelatihan Penyulingan Minyak Atsiri Berbahan Rempah Khas Nusantara

Herbs and Spices are the main wealth of Indonesia which has indeed been known throughout the world. Many countries even import these crops from Indonesia. Spices are a type of plant that has a strong taste and aroma and functions as a spice and flavor enhancer in food. In addition to being used in cooking, spices can also be used as medicines as well as raw materials for herbal medicine. Another form of utilization of these spices is the taking of essential oils found in these spices. This utilization is part of the development of diversification of natural products. The processing of spices into essential oils is one of the other uses with various benefits, as an essential oil, namely an antidote to diseases and other benefits for the health of the human body, and also as an exterminator of several pests and insects. Essential oil processing can be done simply by various groups of people. However, there are still many people who do not know how to properly process essential oils. This Student Service activity is a form of knowledge transfer by the implementing team from the Forest Products Chemistry and Renewable Energy Laboratory, Faculty of Forestry, Mulawarman University, regarding the processing of essential oils and the various properties or benefits of essential oils made from indonesian spices in the hope of increasing the skills of students or the younger generation in processing essential oils and motivating them to open essential oil-based business opportunities from natural ingredients.

The Interaction of Methyl Formate with Proton-Bound Solvent Clusters in the Gas Phase and the Unimolecular Chemistry of the Reaction Products

Ion–molecule reactions between neutral methyl formate (MF) and proton-bound solvent clusters W2H+, W3H+, M2H+, E2H+, and E3H+ (W = water, M = methanol, and E = ethanol) showed that the major reaction product is a solvent molecule loss from the initial encounter complex, followed by the formation of protonated methyl formate (MFH+). Collision-induced dissociation breakdown curves of the initially formed solvent-MF proton-bound pairs and trimers were obtained as a function of collision energy and modeled to extract relative activation energies for the observed channels. Density functional theory calculations (B3LYP/6-311+G(d,p)) of the solvent loss reaction were consistent with barrierless reactions in each case. The MF(M)H+ ion also exhibited loss of CH4 at higher collision energies. The reaction was calculated to proceed via the migration of the MF methyl group to form a loosely bound complex between neutral CH4 and an ion comprising (CH3OH)(CO2)H+. Overall, the results indicate that the interaction of methyl formate with atmospheric water can form stable encounter complexes that will dissociate to form protonated methyl formate.

Ortho‐Quinols in (Bio)Synthesis of Natural Products

Abstract6‐Alkyl‐6‐hydroxycyclohexa‐2,4‐dienone derivatives, commonly referred to as ortho‐quinols, and their simple ester and ether variants constitute a class of organic compounds that aroused much interest amongst chemists over the past 70 years for several reasons related to organic synthesis, natural product chemistry and biochemistry. It was very early on that organic chemists understood the potential of the unique yet versatile chemical reactivity of such compounds to synthesize more complex structures, and it soon emerged that ortho‐quinols could constitute key intermediates in the biosynthesis of certain natural products of various origins. This minireview discusses the chemistry of ortho‐quinols from the point of view of their role in the synthesis and biosynthesis of natural products. Examples of completed syntheses of natural products mostly taken in the literature of the last 20 years or so, together with some chosen pieces from older but pioneering and most remarkable works, are highlighted to illustrate this discussion.

Reaction of the Phytochemistry Community to Green Chemistry: Insights Obtained Since 1990.

This review article aims to study how phytochemists have reacted to green chemistry insights since 1990, the year when the U.S. Environmental Protection Agency launched the "Pollution Prevention Act". For each year in the period 1990 to 2019, three highly cited phytochemistry papers that provided enough information about the experimental procedures utilized were sampled. The "greenness" of these procedures was assessed, particularly for the use of solvents. The highly hazardous diethyl ether, benzene, and carbon tetrachloride did not appear in the papers sampled after 2010. Advances in terms of sustainability were observed mainly in the extraction stage. Similar progress was not observed in purification procedures, where chloroform, dichloromethane, and hexane regularly have been employed. Since replacing such solvents in purification procedures should be a major goal, potential alternative approaches are discussed. Moreover, some current initiatives toward a more sustainable phytochemical research considering aspects other than only solvents are highlighted. Although some advances have been achieved, it is believed that natural products chemists can play a major role in developing a novel ecological paradigm in chemistry. To contribute to this objective, six principles for performing natural products chemistry consistent with the guidelines of green chemistry are proposed.

Dehydrogenative Syntheses of Biazoles via a "Pre-Join" Approach.

The structural motif of biazoles is the predominant substructure of many natural products, pharmaceuticals, and organic materials. Considerable efforts have focused on synthesizing these compounds; however, a limited number of processes have been reported for the efficient formation of biazoles. Herein, we report a "pre-join" approach for the dehydrogenative synthesis of biazoles, which are challenging to prepare using conventional methods. A bench-stable and easily synthesized pyrazine-based group is critical for this transformation. This strategy enables the homocoupling of biazoles and the heterocoupling of two different azoles. Due to the broad substrate scope, this strategy exhibits potential for use in other fields, such as medicine, materials, and natural product chemistry.

Organocatalytic Enantioselective Thermal [4 + 4] Cycloadditions.

Chiral eight-membered carbocycles are important motifs in organic chemistry, natural product chemistry, chemical biology, and medicinal chemistry. The lack of synthetic methods toward their construction is a challenge preventing their rational design and stereoselective synthesis. The catalytic enantioselective [4 + 4] cycloaddition is one of the most straightforward and atom-economical methods to obtain chiral cyclooctadiene derivatives. We report the first organocatalytic asymmetric [4 + 4] cycloaddition of 9H-fluorene-1-carbaldehydes with electron-deficient dienes affording cyclooctadiene derivatives in good yields and with excellent control of peri-, diastereo-, and enantioselectivities. The reaction concept is based on the aminocatalytic formation of a polarized butadiene component incorporated into a cyclic extended π-system, with restricted conformational freedom, allowing for a stereocontrolled [4 + 4] cycloaddition. FMO analysis unveiled that the HOMO and LUMO of the two reacting partners resemble those of butadiene. The methodology allows for the construction of cyclooctadiene derivatives decorated with various functionalities. The cyclooctadienes were synthetically elaborated, allowing for structural diversity demonstrating their synthetic utility for the formation of, for example, chiral cyclobutene- or cyclooctane scaffolds. DFT computational studies shed light on the reaction mechanism identifying the preference for an initial but reversible [4 + 2] cycloaddition delivering an off-cycle catalyst resting state, from which catalyst elimination is not possible. The off-cycle catalyst-bound intermediate undergoes a retro-[4 + 2] cycloaddition, followed by a [4 + 4] cycloaddition generating a cycloadduct from which catalyst elimination is possible. The reaction pathway accounts for the observed peri-, diastereo-, and enantioselectivity of the organocatalytic [4 + 4] cycloaddition.

Discovering New Natural Products Using Metabolomics-Based Approaches.

The incessant search for new natural molecules with biological activities has forced researchers in the field of chemistry of natural products to seek different approaches for their prospection studies. In particular, researchers around the world are turning to approaches in metabolomics to avoid high rates of re-isolation of certain compounds, something recurrent in this branch of science. Thanks to the development of new technologies in the analytical instrumentation of spectroscopic and spectrometric techniques, as well as the advance in the computational processing modes of the results, metabolomics has been gaining more and more space in studies that involve the prospection of natural products. Thus, this chapter summarizes the precepts and good practices in the metabolomics of microbial natural products using mass spectrometry and nuclear magnetic resonance spectroscopy, and also summarizes several examples where this approach has been applied in the discovery of bioactive molecules.

Gas-Phase Fragmentation Reactions of Protonated Pumiliotoxin (+)-251D and Allopumiliotoxin (+)-267A in ESI-MS/MS

In recent years, there has been great interest in understanding the chemistry of natural products from different organisms and their role in ecological processes. Some species of frogs sequester and metabolize dietary alkaloids obtained primarily from mites and ants as chemical defense. Most of these studies have employed gas chromatography techniques coupled with mass spectrometry, which restricts the possibility of observing more polar metabolites. In the case of pumiliotoxin (+)-251D and allopumiliotoxin (+)-267A, the fragmentation mechanisms in electrospray ionization systems with collision-induced fragmentation are undescribed. The present study aims to elucidate the fragmentation pathways of these two toxins. For this purpose, we used direct infusion of toxins in a time-of-flight hyphenated quadrupole electrospray ionization tandem mass spectrometry (ESI-MS/ MS) system. Different collision energies were applied, and the data rationalized from the concepts of reaction mechanisms. The joint analysis allowed to present a robust map of fragmentation opening perspectives for their application in studies of the occurrence of new polar analogues.

C-H modification of natural products: a minimalist enabling tactic for drug discovery, API processing and bioconjugation.

Intrusion into the C-H chemical space of natural products through the strategic deployment of C-H functionalization reactions could lead to incredibly new molecular diversities with an unforeseen impact on biological functions. Based on this hypothesis, semisynthetic C-H modification of natural products is emerging as a minimalist tactic in natural product based drug discovery. Several examples of C-H modification of natural products, resulting in functional gains in key pharmacological attributes viz. potency, aqueous solubility and DMPK profile, along with opportunities in allied areas such as API processing, bioconjugation, and target deconvolution, continue to surface in the recent literature. The strategy has already recorded commercial success in the development of antineoplastic drugs topotecan and irinotecan and in industrial production of pravastatin, calcitriol and artemisinin. This Feature Article highlights the broad contours of this evolving paradigm at the interface of natural product and synthetic chemistry research to accelerate and widen the scope of natural product-based drug discovery.

Metal-free synthesis of dihydrofuran derivatives as anti-vicinal amino alcohol isosteres.

Dihydrofuran cores are commonly incorporated into synthetically and pharmacologically significant scaffolds in natural product and drug discovery chemistry. Herein, we report a concise and practical strategy to construct spiro-dihydrofuran and amino dihydrofuran scaffolds as anti-vicinal amino alcohol isosteres. Hypervalent iodine (PhI(OAc)(NTs2))-mediated C-H activation of alkynes resulted in two-bond formations with one pi bond cleavage: (i) C(sp2)-N(sp3) and O(sp3)-C(sp2); (ii) C(sp2)-N(sp3) and C(sp3)-C(sp2). The metal-free 5-endo-dig oxidative cyclization provided versatile amino 2,3- and 2,5-dihydrofurans bearing the C5 quaternary carbon. The non-toxicity of all synthesised dihydrofurans was verified via in vitro cell viability assay.

Computation-Guided Support to Experiments by the Exploration of Reaction Mechanisms: Organic Synthesis, Natural Products and Environmental Issues

Humankind has experienced a remarkable development since it began to design and optimize chemical reactions to achieve valuable compounds. The key to accomplish these tasks is the proper understanding of how chemical transformations occur at a molecular level, that is, their reaction mechanisms. Based on a suitable mechanistic proposal, experimentalists choose a given chemical protocol to optimize experimental conditions, design new synthetic routes, and circumvent competing reactions. In this context, computational chemistry has become a valuable ally for mechanistic elucidation. We present herein a review of complementary collaborations between experimentalists and theoretical chemists to rationalize processes at the molecular level, focusing mainly on the fields of organic synthesis, natural product chemistry, and systems with environmental interest. Throughout this review, we highlight the ability of computational evaluations to provide answers to questions raised from experiments in a clear and direct way, indicating to experimentalists alternative paths to help them solve their problems.

Natural products with 1,2-oxazine scaffold: occurrence, chemical diversity, bioactivity, synthesis, and biosynthesis.

Covering: up to the end of July, 20231,2-Oxazine is a heterocyclic scaffold rarely found in natural products and is characterized by a directly connected N-O bond in a six-membered ring. Since the discovery of geneserine, the first 1,2-oxazine-containing natural product (1,2-oxazine NP) being isolated from Calabar bean (Physostigma venenosum) in 1925, a total of 76 naturally occurring 1,2-oxazine NPs have been isolated and identified from various sources, which have attracted the attention of researchers in the field of natural product chemistry, organic synthesis, biosynthesis, and pharmacology. This review summarizes the chemical family of 1,2-oxazine NPs, focusing on their source organisms, structural diversities, chemical synthesis, and biosynthesis.

Homeostaza redoks sistema, oksidativni stres i antioksidativni sistem u zdravlju i bolesti - mogućnost modulacije antioksidansima

Redox imbalance occurs when the factors of oxidative stress, known as prooxidants, outweigh the mechanisms of antioxidant protection. In a healthy state, homeostatic mechanisms ensure the balanced production of free radicals and a complete series of antioxidants responsible for their safe removal. The generation of free radicals is a part of physiological processes in a healthy organism, some of which act as specific signaling molecules, and their presence and activity are necessary in these processes. In various diseases such as cancer, cardiovascular disease, diabetes, autoimmune diseases, rheumatic diseases, systemic lupus, and skin diseases, the generation of free radicals overwhelms the protective mechanisms, leading to the development of "oxidative stress" that damages cells and tissues. To prevent the harmful effects of free radicals within cells, there exists a system of enzymatic antioxidant protection composed of superoxide dismutase (SOD), glutathione peroxidase (GSHPx), glutathione reductase (GR), glutaredoxin, reduced/oxidized glutathione (GSH/GSSG), and thioredoxin (TRX). The examples of non-enzymatic antioxidants are: antioxidant vitamins such as A, C and E, dihydrolypoic acid, metallothioneins, ceruloplasmin, coenzyme Q 10, urea, creatinine, etc. Redox balance is influenced by the circadian rhythm and external factors that constitute the "exposome", including dietary habits and lifestyle. Antioxidant supplementation has become increasingly popular for maintaining optimal body function. However, it is important to note that some antioxidants can exhibit prooxidant activity, emphasizing the need for controlled use. The relationship between the redox status of the body and the action of antioxidants enables the development of multidisciplinary research that connects biochemistry, molecular biology, nutritional science, natural product chemistry, and clinical practice.