Principles of odor coding in vertebrates and artificial chemosensory systems.

The biological olfactory system is the sensory system responsible for the detection of the chemical composition of the environment. Several attempts to mimic biological olfactory systems have led to various artificial olfactory systems using different technical approaches. Here we provide a parallel description of biological olfactory systems and their technical counterparts. We start with a presentation of the input to the systems, the stimuli, and treat the interface between the external world and the environment where receptor neurons or artificial chemosensors reside. We then delineate the functions of receptor neurons and chemosensors as well as their overall input-output (I/O) relationships. Up to this point, our accounts of the systems go along similar lines. The next processing steps differ considerably: whereas in biology the processing step following the receptor neurons is the "integration" and "processing" of receptor neuron outputs in the olfactory bulb, this step has various realizations in electronic noses. For a long period of time, the signal processing stages beyond the olfactory bulb, i.e., the higher olfactory centers, were little studied. Only recently has there been a marked growth of studies tackling the information processing in these centers. In electronic noses, a third stage of processing has virtually never been considered. In this review, we provide an up-to-date overview of the current knowledge of both fields and, for the first time, attempt to tie them together. We hope it will be a breeding ground for better information, communication, and data exchange between very related but so far little-connected fields.

Sniffing Out the Sustainable Future: The Renewability Revolution in Fragrance Chemistry.

In this review, the impact of the transition from today's resource-wasting petrochemical economy towards a 100/100 renewable and biodegradable future is discussed with respect to the fragrance families: "citrus", "green", "fruity", "floral", "floriental", "oriental", "woody", "chypre" and "fougère". After benchmark data on ingredients usage, definitions on biodegradation and sustainability are given. Celebrating the 150th anniversary of synthetic vanillin, its historic synthesis from renewable starting materials serves as introduction. In the grand scheme of things, citrus scents upcycled from the beverages industry, are already an ideal case for 100/100 with new opportunities for artificial essential oils. In the fruity domain, transparent and lactonic ingredients are available in a sustainable manner. However, in the domain of green odorants, there is a lack of green chemistry for important key materials. In the floral family, renewability is more critical than biodegradability, but cost is an issue. Thanks to Ambrox and maltol, florientals and orientals will persist, while woody notes severely lack an Iso E Super replacer. In the chypre genre, patchouli became the new moss, but more musks are increasingly in demand. With their high percentage of linalool and dihydromyrcenol, the construction of fougères could well become a precedent for other families, despite challenges in vetiver and salicylates. Still, the challenges exemplified here create immense opportunities for new perfumery materials.

Development of the gas chromatography/mass spectrometry-based aroma designer capable of modifying volatile chemical compositions in complex odors.

Many volatile organic compounds (VOCs) are used to produce various commercial products with aromas mimicking natural products. The VOCs responsible for aromas have been identified from many natural products. The current major strategy is to analyze chemical compositions and aroma qualities of individual VOCs using gas chromatography/mass spectrometry (GC/MS) and GC-olfactometry. However, such analyses cannot determine whether candidate VOCs contribute to the characteristic aroma in mixtures of many VOCs. In this study, we developed a GC/MS-based VOC collection/omission system that can modify the VOC compositions of samples easily and rapidly. The system is composed of GC/MS with a switching unit that can change gas flow routes between MS and a VOC collection device. We first applied this system to prepare gas samples for omission tests, and the aroma qualities of VOC mixtures with and without some VOCs were evaluated by panelists. If aroma qualities were different between the 2 samples, the omitted VOCs were likely key odorants. By collecting VOCs in a gas bag attached to the collection device and transferring some VOCs to MS, specific VOCs could be omitted easily from the VOC mixture. The system could prepare omission samples without chemical identification, preparation of each VOC, and laborious techniques for mixing VOCs, thus overcoming the limitations of previous methods of sample preparation. Finally, the system was used to prepare artificial aromas by replacing VOC compositions between different samples for screening of key odorants. In conclusion, the system developed here can improve aroma research by identifying key odorants from natural products.

Addition of Selected Plant-Derived Semiochemicals to Yellow Sticky Traps Does Not Improve Citrus Psyllid Captures.

Fast and effective monitoring and surveillance techniques are crucial for the swift implementation of control methods to prevent the spread of Huanglongbing, a devastating citrus disease, and its invasive psyllid vector, Asian citrus psyllid, Diaphorina citri, into South Africa, as well as to control the native vector, African citrus triozid, Trioza erytreae. Monitoring for citrus psyllid pests can be improved by using semiochemical odorants to augment already visually attractive yellow sticky traps. However, environmental variables such as temperature and humidity could influence odorant release rates. Five field cages were used to test the ability of a selection of odorants to improve yellow sticky trap efficacy in capturing citrus psyllids. Environmental effects on odorant loss from the dispensers were also investigated. The odorants that most improved yellow sticky trap captures in field cages were then tested under open field conditions alongside lower concentrations of those same lures. Gas chromatography-mass spectrometry was used to calculate odorant release rates as well as to determine if any contamination occurred under field conditions. None of the odorants under field cage or field conditions significantly improved psyllid capture on yellow sticky traps. Temperature influenced odorant loss, and release rate from polyethylene bulbs decreased over time. Based on these results, the use of unbaited yellow sticky traps seems to be the most effective method for monitoring of Huanglongbing vectors.

Application of graphite carbon black assisted-laser desorption ionization-mass spectrometry for soy sauce product discrimination.

In a previous study, we developed a novel analytical method to directly and simultaneously detect taste- and odor-active compounds using graphite carbon black (GCB)-assisted laser desorption ionization mass spectrometry (LDI-MS). In this study, we aimed to evaluate food quality using a variety of soy sauces using the method to discriminate each product. Graphite carbon black-laser desorption ionization-mass spectrometry allowed the provision of hundreds of MS peaks derived from soy sauces in both positive and negative modes without any tedious sample pretreatments. Principal component analysis using the obtained MS peaks clearly distinguished three soy sauce products based on the manufacturing countries (Japan, China, and India). Moreover, this method identified distinct MS peaks for discrimination, which significantly correlated with their quantitative amounts in the products. Thus, GCB-LDI-MS analysis was established as a simple and rapid technique for food analysis, illustrating the chemical patterns of food products.

Role of odorant binding protein C12 in the response of Tribolium castaneum to chemical agents.

Tribolium castaneum is a worldwide pest of stored grain that mainly damages flour, and not only causes serious loss of flour quality but also leads to deterioration of flour quality. Chemical detection plays a key role in insect behavior, and the role of odorant-binding proteins (OBPs) in insect chemical detection has been widely studied. OBPs can interact with small molecule compounds and thereby modulate variation in insecticide susceptibility in insects. In this study, a total of 65 small molecule compounds are selected to investigate the bound effect with TcOBP C12. The molecular docking results showed that ß-caryophyllene, (-)-catechin, butylated hydroxytoluene, diphenyl phthalate and quercetin were the top five compounds, with docking binding energies of -6.11, -5.25, -5.09, -5.05, and - 5.03 Kcal/mol, respectively. Molecular dynamics analysis indicated that odorant binding protein C12 (TcOBP C12) exhibited high binding affinity to all five tested chemical ligands, evidenced by fluorescence quenching assay in vitro. In addition, the contact toxicity assay results suggested that these chemical agents caused a dose-dependent increase in mortality rate for T. castaneum adults. The TcOBP C12 gene was upregulated >2 times after a 24-h exposure, indicating that OBP C12 may play an important role for T. castaneum in response to these chemical agents. In conclusion, our results provide a theoretical basis for future insecticide experiments and pest management.

Changes of Potent Odorants in Salted Duck Egg Yolk before and after Roasting.

As the second most widely consumed eggs, duck eggs are made into preserved eggs, salted duck eggs, and roasted duck eggs to extend their shelf-life. To investigate the differences in potent odorants (POs) between salted duck egg yolk (SDEY) and roasted duck egg yolk (RDEY), the volatiles in SDEY and RDEY were extracted through solvent extraction coupled with solvent-assisted flavor evaporation and were assayed with gas chromatography-mass spectrometry-olfactometry. A total of 45 volatiles were identified in two samples, 24 odor-active compounds (OACs) were screened, and more OACs were in RDEY. The flavor-dilution (FD) factors of OACs were obtained by aroma extract dilution analysis and ranged from 3 to 6561. Twenty-two OACs with FD factors ≥ 9 were quantitated, and the results indicated the concentrations of OACs in yolk increased greatly after salted duck eggs were roasted. Based on the concentrations and thresholds, odor activity values (OAVs) were determined; 17 odorants with OAVs ≥ 1 were determined as POs. Acetoin was the most PO in SDEY; there were more POs in RDEY, including 2-ethyl-3,6-dimethylpyrazine, acetoin, 2-acetyl-3-methylthiophene, dihydro-4-hydroxy-2(3H)-furanone, etc. The outcomes obtained have reference values for making better use of duck eggs in the food industry.

The aroma formation from fresh tea leaves of Longjing 43 to finished Enshi Yulu tea at an industrial scale.

BACKGROUND: Enshi Yulu tea (ESYL) is the most representative of steamed green tea in China, but its aroma formation in processing is unclear. Thus, the ESYL volatiles during the whole industrial processing were investigated using headspace solid-phase microextraction coupled with gas chromatography-mass spectrometry. RESULTS: A total of 134 volatiles were identified. Among these, 31 differential volatiles [P < 0.05 and variable importance in projection (VIP) > 1] and 25 key volatiles [relative odor activity value (rOAV) and/or the ratio of each rOAV to the maximum rOAV (ROAV) > 1.0] were screened out, wherein ß-ionone and nonanal were the most key odorants. Besides, the sensory evaluation combined with multivariate statistical analysis of volatiles pinpointed spreading, fixation, first drying, and second drying as the key processing steps that have a pronounced influence on the aroma quality of ESYL. Furthermore, the oxidative degradation of unsaturated fatty acids, synthesis of monoterpenes, and degradation of carotenoids were the main metabolic pathway for the formation of key odorants. CONCLUSION: The study provides comprehensive insights into the volatile characteristics during the industrial processing of ESYL and promote our understanding of the aroma formation in steamed green teas. © 2024 Society of Chemical Industry.

[Adaptation for use In Russia of the extended odor identification Sniffin' Sticks test]. / Kul'tural'naya adaptatsiya testa na identifikatsiyu zapakhov Sniffin' Sticks dlya ispol'zovaniya v Rossii.

The psychophysical Sniffin' Sticks test, which includes an odor identification test, is the gold standard for assessing the sense of smell in clinical and scientific practice. A necessary requirement for the odor identification test is a close familiarity with the odors used by the inhabitants of the region in which it is used. We studied 77 healthy volunteers and 51 patients with olfactory dysfunction and we found that Russians are not familiar with the three smells from the test (licorice, turpentine and anise) and are completely unfamiliar with the one proposed alternative answer (chives). Moreover, four odors demonstrated very low recognition (less than 75%). The test has been adapted for the use In Russia. In the booklet, licorice is replaced by cough syrup, turpentine by paint thinner, and chives by bay leaf. For odors with low recognition (lemon, apple, pineapple), the alternative fruity odors in the booklet were replaced with more contrasting ones. Based on the data obtained, we are going to develop a domestic version of the odor identification test.

The adsorption of biogenetic odorants onto activated carbon: Adsorption characteristics and impacts of algal organic matter.

Powdered activated carbon (PAC) adsorption is regarded as an efficient method for removing odorants from drinking water. However, in eutrophic aquatic environments, the presence of algal organic matter (AOM) produced by cyanobacteria considerably impedes the adsorption of odorous compounds by activated carbon. This study focused on investigating the adsorption characteristics of three representative odorants: 2-methylisoborneol (2-MIB), ß-cyclocitral (ß-cyclo), and butyl sulfide (BS) by PAC and the effects of AOM on the PAC adsorption of odorants. The removal of the three odorants reached 83.5-97.5% at a PAC dosage of 10 mg/L after 12 h of exposure in a competition-free scenario. The adsorption kinetics demonstrated higher conformity (R2 > 0.9) with the pseudo-second-order model, whereas the adsorption capacity exhibited stronger conformity (R2 > 0.9) with the Freundlich model. The presence of AOM resulted in varying levels of competition for PAC for the adsorption of the three odorants. As the concentration of AOM increased from 0 to 5 mg C/L, the removal of 2-MIB was the most affected (from 83.5% to 10.0%), followed by ß-cyclo (from 86.6% to 55.0%), and BS (from 97.5% to 92.0%). The competitive adsorption of AOM at the molecular level was studied using density functional theory (DFT). The DFT results suggested that odorants with higher and more uniformly distributed electrostatic potentials exhibited a heightened affinity for PAC adsorption and a diminished susceptibility to disruption caused by AOM. This study provides valuable insights into the mitigation of odorous compounds during drinking water purification.

Combining the Classification and Pharmacophore Approaches to Understand Homogeneous Olfactory Perceptions at Peripheral Level: Focus on Two Aroma Mixtures.

The mechanisms involved in the homogeneous perception of odorant mixtures remain largely unknown. With the aim of enhancing knowledge about blending and masking mixture perceptions, we focused on structure-odor relationships by combining the classification and pharmacophore approaches. We built a dataset of about 5000 molecules and their related odors and reduced the multidimensional space defined by 1014 fingerprints representing the structures to a tridimensional 3D space using uniform manifold approximation and projection (UMAP). The self-organizing map (SOM) classification was then performed using the 3D coordinates in the UMAP space that defined specific clusters. We explored the allocating in these clusters of the components of two aroma mixtures: a blended mixture (red cordial (RC) mixture, 6 molecules) and a masking binary mixture (isoamyl acetate/whiskey-lactone [IA/WL]). Focusing on clusters containing the components of the mixtures, we looked at the odor notes carried by the molecules belonging to these clusters and also at their structural features by pharmacophore modeling (PHASE). The obtained pharmacophore models suggest that WL and IA could have a common binding site(s) at the peripheral level, but that would be excluded for the components of RC. In vitro experiments will soon be carried out to assess these hypotheses.

Human ectopic olfactory receptors and their food originated ligands: a review.

Ectopic olfactory receptors (EORs) are expressed in non-nasal tissues of human body. They belong to the G-protein coupled receptor (GPCR) superfamily. EORs may not be capable of differentiating odorants as nasal olfactory receptors (ORs), but still can be triggered by odorants and are involved in different biological processes such as anti-inflammation, energy metabolism, apoptosis etc. Consumption of strong flavored foods like celery, oranges, onions, and spices, is a good aid to attenuate inflammation and boost our immune system. During the digestion of these foods in human digestive system and the metabolization by gut microbiota, the odorants closely interacting with EORs, may play important roles in various bio-functions like serotonin release, appetite regulation etc., and ultimately impact health and diseases. Thus, EORs could be a potential target linking the ligands from food and their bioactivities. There have been related studies in different research fields of medicine and physiology, but still no systematic food oriented review. Our review portrays that EORs could be a potential target for functional food development. In this review, we summarized the EORs found in human tissues, their impacts on health and disease, ligands interacting with EORs exerting specific biological effects, and the mechanisms involved.

Home is Where the Pipeline Ends: Characterization of Volatile Organic Compounds Present in Natural Gas at the Point of the Residential End User.

The presence of volatile organic compounds (VOCs) in unprocessed natural gas (NG) is well documented; however, the degree to which VOCs are present in NG at the point of end use is largely uncharacterized. We collected 234 whole NG samples across 69 unique residential locations across the Greater Boston metropolitan area, Massachusetts. NG samples were measured for methane (CH4), ethane (C2H6), and nonmethane VOC (NMVOC) content (including tentatively identified compounds) using commercially available USEPA analytical methods. Results revealed 296 unique NMVOC constituents in end use NG, of which 21 (or approximately 7%) were designated as hazardous air pollutants. Benzene (bootstrapped mean = 164 ppbv; SD = 16; 95% CI: 134-196) was detected in 95% of samples along with hexane (98% detection), toluene (94%), heptane (94%), and cyclohexane (89%), contributing to a mean total concentration of NMVOCs in distribution-grade NG of 6.0 ppmv (95% CI: 5.5-6.6). While total VOCs exhibited significant spatial variability, over twice as much temporal variability was observed, with a wintertime NG benzene concentration nearly eight-fold greater than summertime. By using previous NG leakage data, we estimated that 120-356 kg/yr of annual NG benzene emissions throughout Greater Boston are not currently accounted for in emissions inventories, along with an unaccounted-for indoor portion. NG-odorant content (tert-butyl mercaptan and isopropyl mercaptan) was used to estimate that a mean NG-CH4 concentration of 21.3 ppmv (95% CI: 16.7-25.9) could persist undetected in ambient air given known odor detection thresholds. This implies that indoor NG leakage may be an underappreciated source of both CH4 and associated VOCs.

Synthesis of Cyclic Fragrances via Transformations of Alkenes, Alkynes and Enynes: Strategies and Recent Progress.

With increasing demand for customized commodities and the greater insight and understanding of olfaction, the synthesis of fragrances with diverse structures and odor characters has become a core task. Recent progress in organic synthesis and catalysis enables the rapid construction of carbocycles and heterocycles from readily available unsaturated molecular building blocks, with increased selectivity, atom economy, sustainability and product diversity. In this review, synthetic methods for creating cyclic fragrances, including both natural and synthetic ones, will be discussed, with a focus on the key transformations of alkenes, alkynes, dienes and enynes. Several strategies will be discussed, including cycloaddition, catalytic cyclization, ring-closing metathesis, intramolecular addition, and rearrangement reactions. Representative examples and the featured olfactory investigations will be highlighted, along with some perspectives on future developments in this area.

Synthesis of odorants in flow and their applications in perfumery.

Continuous flow technology is a key technology for sustainable manufacturing with numerous applications for the synthesis of fine chemicals. In recent years, the preparation of odorants utilizing the advantages of flow reactors received growing attention. In this review, we give an overview of selected methods for the synthesis of odorants in flow, including heterogeneously catalyzed reactions, gas reactions, and photochemical C-H functionalization processes. After a brief introduction on types of odorants, the presented odorant syntheses are ordered according to the main odor families "fruity", "green", "marine", "floral", "spicy", "woody", "ambery", and "musky" and their use and importance for perfumery is briefly discussed.

Data Analytics Determines Co-occurrence of Odorants in Raw Water and Evaluates Drinking Water Treatment Removal Strategies.

A complex dataset with 140 sampling events was generated using triple quadrupole gas chromatography-mass spectrometer to track the occurrence of 95 odorants in raw and finished water from 98 drinking water treatment plants in 31 cities across China. Data analysis identified more than 70 odorants with concentrations ranging from not detected to thousands of ng/L. In raw water, Pearson correlation analysis determined that thioethers, non-oxygen benzene-containing compounds, and pyrazines were classes of chemicals that co-occurred, and geosmin and p(m)-cresol, as well as cyclohexanone and benzaldehyde, also co-occurred, indicating similar natural or industrial sources. Based on classification and regression tree analysis, total dissolved organic carbon and geographical location were identified as major factors affecting the occurrence of thioethers. Indoles, phenols, and thioethers were well-removed through conventional and advanced treatment processes, while some aldehydes could be generated. For other odorants, higher removal was achieved by ozonation-biological activated carbon (39.3%) compared to the conventional treatment process (14.5%). To our knowledge, this is the first study to systematically identify the major odorants in raw water and determine suitable treatment strategies to control their occurrence by applying data analytics and statistical methods to the complex dataset. These provide informative reference for odor control and water quality management in drinking water industry.

Molecular background of the undesired odor of polypropylene materials and insights into the sources of key odorants.

Screening the volatiles isolated from a standard polypropylene material consisting of a polypropylene homopolymer, the filler talcum, and a mixture of antioxidants, for odor-active compounds by application of an aroma extract dilution analysis revealed 30 odorants with flavor dilution factors ranging from 1 to 64. Eighteen odor-active compounds were subsequently quantitated by gas chromatography-mass spectrometry using stable isotopically substituted odorants as internal standards, and their odor activity values (OAVs) were calculated as ratios of the concentrations to the odor threshold values. Five odorants showed OAVs ≥1, among which were hex-1-en-3-one (OAV 12), butanoic acid (OAV 3), as well as 4-methylphenol, butan-1-ol, and 2-tert-butylphenol (all OAV 1). A comparative analysis of polypropylene materials with different additives suggested plastic-like, pungent smelling hex-1-en-3-one as an ubiquitous key odorant. Odor-active amounts of alkylphenols, in particular plastic-like, phenolic smelling 2-tert-butylphenol, were additionally formed in the presence of talcum and phenolic antioxidants. Whereas the precursors of the phenols were thus obvious, the origin of hex-1-en-3-one was unknown. Injection molding showed only little influence on odorant concentrations.

Characterization of Key Odorants in Scallion Pancake and Investigation on Their Changes during Storage.

To characterize key odorants in scallion pancake (SP), volatiles were extracted by solvent extraction-solvent assisted flavor evaporation. A total of 51 odor-active compounds were identified by gas chromatography-olfactometry (GC-O) and chromatography-mass spectrometry (GC-MS). (Z/E)-3,6-Diethyl-1,2,4,5-tetrathiane was detected for the first time in scallion food. Application of aroma extract dilution analysis to extracts showed maltol, methyl propyl disulfide, dipropyl disulfide and 2-pentylfuran had the highest flavor dilution (FD) factor of 4096. Twenty-three odorants with FD factors ≥ 8 were quantitated, and their odor active values (OAVs) were calculated. Ten compounds with OAVs ≥ 1 were determined as the key odorants; a recombinate model prepared from the key odorants, including (E,E)-2,4-decadienal, dimethyl trisulfide, methyl propyl disulfide, hexanal, dipropyl trisulfide, maltol, acetoin, 2-methylnaphthalene, 2-pentylfuran and 2(5H)-furanone, successfully simulated the overall aroma profile of SP. The changes in odorants during storage were investigated further. With increasing concentrations and OAVs during storage, hexanal became an off-flavor compound.

Characterization of the Aroma Profile and Main Key Odorants of Espresso Coffee.

Espresso coffee (EC) is a common coffee preparation technique that nowadays is broadly widespread all over the globe. Its popularity is in part attributed to the intense aroma and pleasant flavor. Many researchers have studied and reviewed the aroma of the coffee, but there is a lack of specific review focused on EC aroma profile even if it is intensively investigated. Thus, the objective of the current review was to summarize the aroma profile of EC and how different preparation variables can affect EC flavor. Moreover, a collection of diverse analytical procedures for volatile analysis was also reported. The findings of this survey showed that the volatile fraction of EC is extremely complex, but just some compounds are responsible for the characteristic aroma of the coffee, such as some aldehyde, ketones, furanones, furans, sulfur compounds, pyrazines, etc. In addition, during preparation, some variables, e.g., temperature and pressure of water, granulometry of the coffee particle, and brew ratio, can also modify the aroma profile of this beverage, and therefore its quality. A better understanding of the aroma fraction of EC and how the preparation variables should be adjusted according to desired EC would assist coffee workers in obtaining a higher quality product.

Methyl-Cyclohexane Methanol (MCHM) Isomer-Dependent Binding on Amorphous Carbon Surfaces.

In January 2014, over 10,000 gallons of methyl-cyclohexane methanol (MCHM) leaked into the Elk River in West Virginia, in a chemical spill incident that contaminated a large portion of the state's water supply and left over 300,000 residents without clean water for many days and weeks. Initial efforts to remove MCHM at the treatment plant centered on the use of granulated activated carbon (GAC), which removed some of the chemical from the water, but MCHM levels were not lowered to a "non-detect" status until well after the chemical plume had moved downstream of the intake. Months later, MCHM was again detected at the outflow (but not the inflow) at the water treatment facility, necessitating the full and costly replacement of all GAC in the facility. The purpose of this study is to investigate the hypothesis that preferential absorbance of one of the two MCHM isomers, coupled with seasonal variations in water temperature, explain this contrary observation. Calculated intermolecular potentials between ovalene (a large planar polycyclic aromatic hydrocarbon) and the MCHM isomers were compared to physisorption potentials of MCHM onto an amorphous carbon model. While a molecular mechanics (MM) force field predicts no difference in the average interaction potentials between the cis- and trans-MCHM with the planar ovalene structure, MM predicts that the trans isomer binds stronger than the cis isomer to the amorphous carbon surface. Semi-empirical and density functional theory also predict stronger binding of trans-MCHM on both the planar and amorphous surfaces. The differences in the isomer binding strengths on amorphous carbon imply preferential absorbance of the trans isomer onto activated charcoal filter media. Considering seasonal water temperatures, simple Arrhenius kinetics arguments based on these predicted binding energies help explain the environmental observations of MCHM leeching from the GAC filters months after the spill. Overall, this work shows the important implications that can arise from detailed interfacial chemistry investigations.