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A series of binuclear rare‐earth metal complexes based on the ligands containing bis(phosphinophenyl)amido‐PNP unit are successfully synthesized. All the ligands and the corresponding binuclear complexes are fully characterized by NMR spectra (1H, 13C, and 31P). In conjunction with [Ph3C][B(C6F5)4], all the binuclear complexes exhibited high catalytic activity and high cis‐1,4‐selectivity (>99%) toward the polymerization of 1,3‐conjugated dienes (isoprene, β‐myrcene and β‐farnesene) with excellent livingness at room temperature or even 80 °C. [ABSTRACT FROM AUTHOR]

Terpenoids are a large class of natural secondary plant metabolites which are highly diverse in structure, formed from isoprene units (C-5), associated with a wide range of biological properties, including antioxidant, antimicrobial, anti-inflammatory, antiallergic, anticancer, antimetastatic, antiangiogenesis, and apoptosis induction, and are considered for potential application in the food, cosmetics, pharmaceutical, and medical industries. In plants, terpenoids exert a variety of basic functions in growth and development. This review gives an overview, highlighting the current knowledge of terpenoids and recent advances in our understanding of the organization, regulation, and diversification of core and specialized terpenoid metabolic pathways and addressing the most important functions of volatile and non-volatile specialized terpenoid metabolites in plants. A comprehensive description of different aspects of plant-derived terpenoids as a sustainable source of bioactive compounds, their biosynthetic pathway, the several biological properties attributed to these secondary metabolites associated with health-promoting effects, and their potential industrial applications in several fields will be provided, and emerging and green extraction methods will also be discussed. In addition, future research perspectives within this framework will be highlighted. Literature selection was carried out using the National Library of Medicine, PubMed, and international reference data for the period from 2010 to 2024 using the keyword "terpenoids". A total of 177,633 published papers were found, of which 196 original and review papers were included in this review according to the criteria of their scientific reliability, their completeness, and their relevance to the theme considered. [ABSTRACT FROM AUTHOR]

Biogenic hydrocarbons are emitted into the Earth's atmosphere by terrestrial vegetation as by‐products of photosynthesis. Isoprene is one such hydrocarbon and is the second most abundant volatile organic compound emitted into the atmosphere (after methane). Reaction with ozone represents an important atmospheric sink for isoprene removal, forming carbonyl oxides (Criegee intermediates) with extended conjugation. In this manuscript, we argue that the extended conjugation of these Criegee intermediates enables electronic excitation of these compounds, on timescales that are competitive with their slow unimolecular decay and bimolecular chemistry. We show that the complexation of methacrolein oxide with water enhances the absorption cross section of the otherwise dark S1 state, potentially revealing a new avenue for forming lower volatility compounds via tropospherically relevant photochemistry. [ABSTRACT FROM AUTHOR]

Introduction: This study employs Proton-Transfer-Reaction Mass Spectrometry (PTR-MS) to analyze exhaled breath profiles of 504 healthy adults, focusing on nine common volatile organic compounds (VOCs): acetone, acetaldehyde, acetonitrile, ethanol, isoprene, methanol, propanol, phenol, and toluene. PTR-MS offers real-time VOC measurement, crucial for understanding breath biomarkers and their applications in health assessment. Objectives: The study aims to investigate how demographic factors-gender, age, and smoking history-affect VOC concentrations in exhaled breath. The objective is to enhance our understanding of breath biomarkers and their potential for health monitoring and clinical diagnosis. Methods: Exhaled breath samples were collected using PTR-MS, measuring concentrations of nine VOCs. The data were analyzed to discern distribution patterns across demographic groups. Results: Males showed higher average VOC levels for certain compounds. Propanol and methanol concentrations significantly increased with age. Smoking history influenced VOC levels, with differences among non-smokers, current smokers, and ex-smokers. Conclusion: This research provides valuable insights into demographic influences on exhaled VOC profiles, emphasizing the potential of breath analysis for health assessment. PTR-MS's real-time measurement capabilities are crucial for capturing dynamic VOC changes, offering advantages over conventional methods. These findings lay a foundation for advancements in non-invasive disease detection, highlighting the importance of considering demographics in breath biomarker research. [ABSTRACT FROM AUTHOR]

Isoprene is a common monomer in industrial synthetic rubber. We report the in vitro synthesis of isoprene in a multi-step enzyme cascade immobilized biocatalyst by the mevalonate pathway (MVA pathway). This method offers a new way for expanding the biosynthesis of isoprene. The cascade immobilized biocatalyst (PE-SBA-15-FiEs) was constructed by adsorption- cross-linking, with the five key enzymes (mevalonate kinase (MVK), phosphomevalonate kinase (PMK), Mevalonate diphosphate decarboxylase (MVD), isopentenyl disphosphate isomerase (IDI), and isoprene synthetase (ISPS)) of the MVA pathway immobilized on mesoporous molecular sieve SBA-15 as the carrier with polyethylene glycol diglycidyl ether as the cross-linker. At the optimal reaction pH and temperature, the yield of isoprene reached 453.15 mg/L with the PE-SAB-15-FiE, as compared to 274.52 mg/L with the free enzymes. After it had been used five times, the yield of isoprene was still 404.26 mg/L. Furthermore, the yield of isoprene still reached 372.59 mg/L when it was stored for 30 days at room temperature. Thus, the assembled PE-SBA-15-FiEs cascade immobilized biocatalyst has promising application prospects for the industrial production of isoprene. [ABSTRACT FROM AUTHOR]

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Within the context of Molecular Electronic Density Theory (MEDT), this study investigates the Diels–Alder reaction among isoprene (2) and R-carvone (1R) applying DFT simulations, with and without Lewis acid (LA) catalysis. The results show that carvone (1R) acts as an electrophile and isoprene (2) as a nucleophile in a polar process. LA catalysis increases the electrophilicity of carvone, thereby improving the reactivity and selectivity of the reaction by reducing the activation Gibbs free energy. Parr functions reveal that the C5=C6 double bond is more reactive than the C9=C10 double bond, indicating chemoselectivity. The examination of the Electron Localization Function (ELF) reveals high regio- and stereoselectivity, indicating an asynchronous mechanism for the LA-catalyzed DA reaction. Furthermore, it is suggested that cycloadduct 3 has great anti-HIV potential because it exhibits lower binding energies than azidothymidine (AZT) in the docking studies of cycloadducts 3 and 4 amongst a primary HIV-1protein (1A8O plus 5W4Q). [ABSTRACT FROM AUTHOR]

It has been widely reported that isoprene emissions from the Arctic ecosystem have a strong temperature response. Here we identify sedges (Carex spp. and Eriophorum spp.) as key contributors to this high sensitivity using plant chamber experiments. We observe that sedges exhibit a markedly stronger temperature response compared to that of other isoprene emitters and predictions by the widely accepted isoprene emission model, the Model of Emissions of Gases and Aerosols from Nature (MEGAN). MEGAN is able to reproduce eddy-covariance flux observations at three high-latitude sites by integrating our findings. Furthermore, the omission of the strong temperature responses of Arctic isoprene emitters causes a 20% underestimation of isoprene emissions for the high-latitude regions of the Northern Hemisphere during 2000-2009 in the Community Land Model with the MEGAN scheme. We also find that the existing model had underestimated the long-term trend of isoprene emissions from 1960 to 2009 by 55% for the high-latitude regions. The authors identify that sedges in the Arctic have a different isoprene temperature response than other temperate plants, and this finding explains the high temperature sensitivity of isoprene emissions from Arctic terrestrial ecosystems. [ABSTRACT FROM AUTHOR]

A series of bis(oxazoline) rare-earth metal dialkyl complexes [(L)Ln(CH2SiMe3)2(THF)n] (L = L1 (dimethyl-substituted bis(oxazoline) ligand), Ln = Y (1-Y), Lu (1-Lu), Sc (1-Sc), n = 1; L = L2 (phenyl-substituted bis(oxazoline) ligand), Ln = Y (2-Y), Lu (2-Lu), Sc (2-Sc), n = 2) was successfully prepared. NMR spectroscopy and X-ray diffraction indicated that all the complexes ligated with a C2 symmetric bis(oxazoline) and two trimethylsilylmethyl ligands. In the presence of borate and triisobutyl aluminium, these complexes exhibited high catalytic activity for the polymerization of isoprene, yielding the polymer with high cis-1,4-regularity (up to 99.9%) and high molecular weight. Moreover, these ternary catalytic systems also served as efficient initiators for the polymerization of polar ortho-methoxystyrene. However, atactic polymers in all the cases were isolated despite the C2 symmetric geometry of bis(oxazoline) ligands. [ABSTRACT FROM AUTHOR]

We report new method of isoprene heterogeneous polymerization utilizing late lanthanide based catalyst and supported by a polysiloxane covered nanoparticles (nanodiamonds). The corresponding heterogeneous neodymium catalysts demonstrated superior properties in isoprene polymerization giving one and a half times higher molecular weight of resulting polymers comparing to homogeneous polymerization using the same catalyst. The part of cis-1,4 units in resulting polymers is up to 97.5%. Importantly, this strategy can achieve polymer nanocomposites with excellent distribution of nanofillers and satisfactory mechanical performance. [ABSTRACT FROM AUTHOR]

Isoprene pyrophosphates play a crucial role in the synthesis of a diverse array of essential nonsterol and sterol biomolecules and serve as substrates for posttranslational isoprenylation of proteins, enabling specific anchoring to cellular membranes. Hydrolysis of isoprene pyrophosphates would be a means to modulate their levels, downstream products, and protein isoprenylation. While NUDIX hydrolases from plants have been described to catalyze the hydrolysis of isoprene pyrophosphates, homologous enzymes with this function in animals have not yet been reported. In this study, we screened an extensive panel of human NUDIX hydrolases for activity in hydrolyzing isoprene pyrophosphates. We found that human nucleotide triphosphate diphosphatase NUDT15 and 8‐oxo‐dGDP phosphatase NUDT18 efficiently catalyze the hydrolysis of several physiologically relevant isoprene pyrophosphates. Notably, we demonstrate that geranyl pyrophosphate is an excellent substrate for NUDT18, with a catalytic efficiency of 2.1 × 105 m−1·s−1, thus making it the best substrate identified for NUDT18 to date. Similarly, geranyl pyrophosphate proved to be the best isoprene pyrophosphate substrate for NUDT15, with a catalytic efficiency of 4.0 × 104 M−1·s−1. LC–MS analysis of NUDT15 and NUDT18 catalyzed isoprene pyrophosphate hydrolysis revealed the generation of the corresponding monophosphates and inorganic phosphate. Furthermore, we solved the crystal structure of NUDT15 in complex with the hydrolysis product geranyl phosphate at a resolution of 1.70 Å. This structure revealed that the active site nicely accommodates the hydrophobic isoprenoid moiety and helped identify key binding residues. Our findings imply that isoprene pyrophosphates are endogenous substrates of NUDT15 and NUDT18, suggesting they are involved in animal isoprene pyrophosphate metabolism. [ABSTRACT FROM AUTHOR]

Nanoparticle reinforcement is a general approach toward the strengthening of elastomer nanocomposite in large‐scale applications. Extensive studies and efforts have been contributed to demonstrating the property reinforcement of polymer nanocomposites in relation to matrix‐filler and filler‐filler interaction. Here, a facile synthetic method is creatively reported to synthesize SiO2,15/120‐g‐polyisoprene (SiO2‐g‐PI) particle brushes using atom transfer radical polymerization (ATRP). The dispersion and microstructures of the nanoparticles in the nanocomposites are investigated by morphological characterizations, whereas the reinforcing mechanism is studied through mechanical measurements as well as computational simulation. Remarkably, compared with the cured bulk elastomers and matrix(M)/SiO2 blends, M/particle brushes (PB) exhibit significant improvement in mechanical properties, including tensile strength, elongation at break, modules, and rolling resistance. This elastomer nanocomposites afford a novel prospect for the practical application of next‐generation automobile tires with enhanced performance. [ABSTRACT FROM AUTHOR]

Accurately measuring emission factors (Es) of biogenic volatile organic compounds (BVOCs) with consideration of intraspecific variability is vital but often overlooked. This study presents in‐situ measurements of BVOC emissions from 114 Eucalyptus urophylla individuals using the LI‐6800 portable photosynthesis system. We observed intraspecific variability exceeding an order of magnitude in BVOC Es. Despite this variability, our approach yielded statistically representative Es for E. urophylla, yet challenging the feasibility of extensive field measurements. By quickly screening net photosynthesis rate (Pn) across a broad set of individuals and selecting those within a specific Pn range, such as mean ± 0.1 × SD (standard deviation) of Pn for all screened individuals, for detailed BVOC emission measurements, we achieved comparable mean Es with approximately 10% of the original sampling effort. This offers a practical solution for efficient and accurate field measurement of representative BVOC Es, significantly reducing required sample size while effectively addressing intraspecific variability. Plain Language Summary: Quantifying the emission of volatile organic compounds, such as isoprene, by trees is important yet poses significant challenges, particularly due to the variability observed within a single species. In our study, we used a portable devise to measure these emissions from 114 Eucalyptus urophylla trees within the same plantation, uncovering variances that spanned more than tenfold. Given the impracticality of measuring such a large number of trees to obtain statistically representative emissions data that accounts for intraspecific variability, we proposed a simpler way to get accurate measurements by strategically selecting a smaller subset of trees. This method drastically cuts down the effort and time needed for such studies, making it easier to gather reliable data in natural environments. Key Points: Biogenic volatile organic compound (BVOC) emission factors (Es) for 114 Eucalyptus urophylla individuals were measured in situIntraspecific variation in Es of BVOC exceeded an order of magnitude, with average Es statistically representativeA novel method was introduced for fast, accurate and efficient measurement of representative Es of BVOC with reduced sample size [ABSTRACT FROM AUTHOR]

Biogenic volatile organic compounds (BVOCs) are important precursors of forming ozone (O3) and secondary organic aerosols (SOAs), which have important impacts on air quality and climate change. Using a literature search, this review analyzed the concentration levels and spatial-temporal distributions of isoprene and monoterpene in the atmosphere in China, mainly from biogenic emissions, and estimated their impact on O3 and SOA generation. The existing observations were mainly in the Beijing–Tianjin–Hebei region, the Pearl River Delta region, central China, and in remote mountainous areas. The results showed that isoprene is the dominant component of BVOCs in the atmosphere, and its ambient concentration is much higher than monoterpene. The site-average concentrations of isoprene and monoterpene were 0.004–3.80 and 0.0003–6.31 ppb, respectively. At vegetation sites, the concentrations of isoprene and monoterpene were 0.006–3.80 and 0.007–6.31 ppb, respectively, whereas they were 0.004–2.70 and 0.0003–1.10 ppb at urban sites. For urban sites, the higher concentrations of annual isoprene occurred mainly in several central megacities, in the Sichuan–Chongqing region, and in southern regions. For vegetation sites, higher concentrations mainly occurred in southern regions. Ambient concentrations of BVOCs in the western region were the lowest for both urban and vegetation sites. Both isoprene and monoterpene showed higher concentrations in summer. The potential of isoprene and monoterpene to form O3 was 0.05–57.21 and 0.003–72.35 ppb, while that which form SOA was 0.0002–0.21 and 0.0006–10.46 µg/m3, respectively. For urban sites, the average annual O3 formation potential (OFP) by isoprene and monoterpene was 8.70 and 2.58 ppb, respectively, and their SOA formation potential (SOAP) was 0.03 and 0.37 µg/m3, respectively. For vegetation sites, it was 7.95 and 5.31 ppb and 0.03 and 0.75 µg/m3, respectively. The annual average contributions of isoprene and monoterpene to O3 and SOA formation were higher in the Beijing–Tianjin–Hebei region, Pearl River Delta region, and central China, which experience severe air pollution in China. [ABSTRACT FROM AUTHOR]

Terpenoids have extensive pharmacological activities and are extensively applied in the pharmaceutical, cosmetic, and food industries. Increasing the structural diversity of terpenoids would expand their potential applications. Noncanonical backbones can be generated by coexpressing the canonical mevalonate pathway and C-methyltransferases, or the lepidopteran mevalonate pathway, in engineered strains. The design and chemical synthesis of farnesyl pyrophosphate analogs to create unnatural terpenoids promises two advantages: it complements other methods of terpene synthesis and bypasses the task of engineering entire metabolic pathways to produce alternative substrates in vivo. The artificial metalloenzyme Ir(Me)-porphyrin IX CYP119 allows cyclopropanation of limonene to synthesize high titers of unnatural products with high diastereoselectivity. Terpenoids display chemical and structural diversities as well as important biological activities. Despite their extreme variability, the range of these structures is limited by the scope of natural products that canonically derive from interconvertible five-carbon (C5) isoprene units. New approaches have recently been developed to expand their structural diversity. This review systematically explores the combinatorial biosynthesis of noncanonical building blocks via the coexpression of the canonical mevalonate (MVA) pathway and C-methyltransferases (C-MTs), or by using the lepidopteran mevalonate (LMVA) pathway. Unnatural terpenoids can be created from farnesyl diphosphate (FPP) analogs by chemobiological synthesis and terpene cyclopropanation by artificial metalloenzymes (ArMs). Advanced technologies to accelerate terpene biosynthesis are discussed. This review provides a valuable reference for increasing the diversity of valuable terpenoids and their derivatives, as well as for expanding their potential applications. [ABSTRACT FROM AUTHOR]

Oceanic biogenic emissions exert a significant impact on the atmospheric environment within the marine boundary layer (MBL). This study employs the extreme gradient boosting (XGBoost) machine learning method and clustering method combined with satellite observations and model simulations to discuss the effects of marine biogenic emissions on MBL formaldehyde (HCHO). The study reveals that HCHO columnar concentrations peaked in summer with 8.25 × 1015 molec/cm2, but the sea–air exchange processes controlled under the wind and sea surface temperature (SST) made marine biogenic emissions represented by isoprene reach their highest levels in winter with 95.93 nmol/m2/day. Analysis was conducted separately for factors influencing marine biogenic emissions and affecting MBL HCHO. It was found that phytoplankton functional types (PFTs) and biological degradation had a significant impact on marine biogenic emissions, with ratio range of 0.07~15.87 and 1.02~5.42 respectively. Machine learning methods were employed to simulate the conversion process of marine biogenic emissions to HCHO in MBL. Based on the SHAP values of the learning model, the importance results indicate that the factors influencing MBL HCHO mainly included NO2, as well as temperature (T) and relative humidity (RH). Specifically, the influence of NO2 on atmospheric HCHO was 1.3 times that of T and 1.6 times that of RH. Wind speed affected HCHO by influencing both marine biogenic emission and the atmospheric physical conditions. Increased marine biogenic emissions in air masses heavily influenced by human activities can reduce HCHO levels to some extent. However, in areas less affected by human activities, marine biogenic emissions can lead to higher levels of HCHO pollution. This research explores the impact of marine biogenic emissions on the HCHO status of the MBL under different atmospheric chemical conditions, offering significant insights into understanding chemical processes in marine atmospheres. [ABSTRACT FROM AUTHOR]

Chardonnay is a non-floral grape with economic value and nutritional properties that is widely grown in northwestern China. However, limited research has been conducted on exogenous spraying to regulate volatile compound metabolism (especially isoprene metabolism) in Chardonnay grapes. Benzothiadiazole (BTH) can induce disease resistance and augment the contents of phenolics and volatile compounds in grapes. This study aimed to evaluate the influence of BTH on the accumulation of isoprene aroma, carotenoid levels and the activity profiles of key enzymes. Chardonnay grapevines were treated with 0.37 mM BTH at veraison to investigate the impact on physicochemical parameters, carotenoids, metabolic enzyme activities, and free and bound isoprenoids in developing Chardonnay grapes. The results showed that reducing sugars, and total soluble solids of BTH-treated grapes increased, while the content of titratable acidity, β-carotene, zeaxanthin, β-cryptoxanthin, chlorophyll, and total carotenoids in treated ripe grapes decreased relative to control berries. BTH-treated ripe grapes exhibited elevated levels of bound norisoprenoids and three key enzemy activities (carotenoid cleavage dioxygenase, phytoene synthase, lycopene β-cyclase), with a slight decrease in free norisoprenoids. Free and bound terpenoids profiles were also significantly enhanced by BTH treatment at veraison. Our findings offer novel perspectives into the modulation of isoprene biosynthesis in grape berries when exposed to BTH. [ABSTRACT FROM AUTHOR]

The statistical anionic copolymerization of 4‐trimethylsilylstyrene (TMSS) with isoprene (I) in cyclohexane was investigated using in situ near‐infrared (NIR) spectroscopy in the presence of various amounts of the polar modifier tetrahydrofuran (THF). Polymers with narrow molecular weight distribution of 85–138 kg/mol and dispersities of 1.09–1.22 were obtained. By increasing modifier content, the reactivity ratios can be adjusted over a wide range from rTMSS < rI to rTMSS >> rI. Compared to the system styrene/isoprene (S/I) only a minute amount of modifier (0.5 eq THF relative to lithium) is sufficient to alter the reactivity ratios, resulting in an ideally random copolymerization, which validates the higher reactivity of TMSS compared to styrene. Using these reactivity ratios, molar and volume composition gradients were calculated. Additionally, the glass transition temperature and microstructure of the polyisoprene units were investigated via differential scanning calorimetry and proton nuclear magnetic resonance. The results are encouraging for the use of these materials in high‐end applications like membranes. [ABSTRACT FROM AUTHOR]

At present, vulcanization is an indispensable process in rubber industries and ZnO is an important ingredient in vulcanization reactions. However, ZnO is toxic to aquatic organisms and the use of ZnO is unfavorable to the sustainable development of rubber industry. The decrease of ZnO content without the reduction in properties of rubbers has been an open question in rubber industries. In this work, our group designs nucleophiles with an ability to open the ring of sulfur. With the decrease of ZnO content, the addition of nucleophiles maintains the ring‐opening capacity of sulfur. As a result, changes in several properties of rubbers such as tensile strength, tear strength, and crosslinking density are negligible with the reduction of ZnO content. Also, the thermo‐oxidative resistance of rubbers improves dramatically with the decrease of ZnO content and addition of nucleophiles. Through designing nucleophiles to reduce the content of ZnO, this work provides a strategy to develop sustainable rubber industries. [ABSTRACT FROM AUTHOR]

Isoprene has the largest global non-methane hydrocarbon emission, and the oxidation of isoprene plays a crucial role in the formation of secondary organic aerosol (SOA). Two primary processes are known to contribute to SOA formation from isoprene oxidation: (1) the reactive uptake of isoprene-derived epoxides on acidic or aqueous particle surfaces and (2) the absorptive gas–particle partitioning of low-volatility oxidation products. In this study, we developed a new multiphase condensed isoprene oxidation mechanism that includes these processes with key molecular intermediates and products. The new mechanism was applied to simulate isoprene gas-phase oxidation products and SOA formation from previously published chamber experiments under a variety of conditions and atmospheric observations during the Southern Oxidant and Aerosol Studies (SOAS) field campaign. Our results show that SOA formation from most of the chamber experiments is reasonably reproduced using our mechanism, except when the concentration ratios of initial nitric oxide to isoprene exceed ∼ 2, the formed SOA is significantly underpredicted. The SOAS simulations also reasonably agree with the measurements regarding the diurnal pattern and concentrations of different product categories, while the total isoprene SOA remains underestimated. The molecular compositions of the modeled SOA indicate that multifunctional low-volatility products contribute to isoprene SOA more significantly than previously thought, with a median mass contribution of ∼ 57 % to the total modeled isoprene SOA. However, this contribution is intricately intertwined with IEPOX-derived SOA (IEPOX: isoprene-derived epoxydiols), posing challenges for their differentiation using bulk aerosol composition analysis (e.g., the aerosol mass spectrometer with positive matrix factorization). Furthermore, the SOA from these pathways may vary greatly, mainly dependent on the volatility estimation and treatment of particle-phase processes (i.e., photolysis and hydrolysis). Our findings emphasize that the various pathways to produce these low-volatility species should be considered in models to more accurately predict isoprene SOA formation. The new condensed isoprene chemical mechanism can be further incorporated into regional-scale air quality models, such as the Community Multiscale Air Quality Modelling System (CMAQ), to assess isoprene SOA formation on a larger scale. [ABSTRACT FROM AUTHOR]

The asymmetric Diels–Alder reaction of chalcone and isoprene has been accomplished by use of chiral titanium complexes. Notably, an enantiomeric excess as high as 61% and a regioselectivity of 95% have been achieved. The preparation of the chiral titanium complexes is simple and does not require the pre-installation of a chiral auxiliary. This study represents the first example of asymmetric Diels–Alder reaction between chalcone and isoprene. [ABSTRACT FROM AUTHOR]

The plastidic 2-C-methylerythritol 4-phosphate (MEP) pathway supplies the precursors of a large variety of essential plant isoprenoids, but its regulation is still not well understood. Using metabolic control analysis (MCA), we examined the first enzyme of this pathway, 1-deoxyxylulose 5-phosphate synthase (DXS), in multiple grey poplar (Populus × canescens) lines modified in their DXS activity. Single leaves were dynamically labeled with 13CO2 in an illuminated, climate-controlled gas exchange cuvette coupled to a proton transfer reaction mass spectrometer, and the carbon flux through the MEP pathway was calculated. Carbon was rapidly assimilated into MEP pathway intermediates and labeled both the isoprene released and the IDP+DMADP pool by up to 90%. DXS activity was increased by 25% in lines overexpressing the DXS gene and reduced by 50% in RNA interference lines, while the carbon flux in the MEP pathway was 25–35% greater in overexpressing lines and unchanged in RNA interference lines. Isoprene emission was also not altered in these different genetic backgrounds. By correlating absolute flux to DXS activity under different conditions of light and temperature, the flux control coefficient was found to be low. Among isoprenoid end products, isoprene itself was unchanged in DXS transgenic lines, but the levels of the chlorophylls and most carotenoids measured were 20–30% less in RNA interference lines than in overexpression lines. Our data thus demonstrate that DXS in the isoprene-emitting grey poplar plays only a minor part in controlling flux through the MEP pathway. [ABSTRACT FROM AUTHOR]

Isoprene, a key biogenic volatile organic compound, plays a pivotal role in atmospheric chemistry. Due to its high reactivity, this compound contributes significantly to the production of tropospheric ozone in polluted areas and to the formation of secondary organic aerosols. The assessment of biogenic emissions is of great importance for regional and global air quality evaluation. In this study, we implemented the biogenic emission model MEGANv2.1 (Model of Emissions of Gases and Aerosols from Nature, version 2.1) in the surface model SURFEXv8.1 (SURface EXternalisée in French, version 8.1). This coupling aims to improve the estimation of biogenic emissions using the detailed vegetation-type-dependent treatment included in the SURFEX vegetation ISBA (Interaction between Soil Biosphere and Atmosphere) scheme. This scheme provides vegetation-dependent parameters such as leaf area index and soil moisture to MEGAN. This approach enables a more accurate estimation of biogenic fluxes compared to the stand-alone MEGAN model, which relies on average input values for all vegetation types. The present study focuses on the assessment of the SURFEX–MEGAN model isoprene emissions. An evaluation of the coupled SURFEX–MEGAN model results was carried out by conducting a global isoprene emission simulation in 2019 and by comparing the simulation results with other MEGAN-based isoprene inventories. The coupled model estimates a total global isoprene emission of 443 Tg in 2019. The estimated isoprene is within the range of results obtained with other MEGAN-based isoprene inventories, ranging from 311 to 637 Tg. The spatial distribution of SURFEX–MEGAN isoprene is consistent with other studies, with some differences located in low-isoprene-emission regions. Several sensitivity tests were conducted to quantify the impact of different model inputs and configurations on isoprene emissions. Using different meteorological forcings resulted in a ± 5 % change in isoprene emissions using MERRA (Modern-Era Retrospective analysis for Research and Applications) and IFS (Integrated Forecasting System) compared with ERA5. The impact of using different emission factor data was also investigated. The use of PFT (plant functional type) spatial coverage and PFT-dependent emission potential data resulted in a 12 % reduction compared to using the isoprene emission potential gridded map. A significant reduction of around 38 % in global isoprene emissions was observed in the third sensitivity analysis, which applied a parameterization of soil moisture deficit, particularly in certain regions of Australia, Africa, and South America. The significance of coupling the SURFEX and MEGAN models lies particularly in the ability of the coupled model to be forced with meteorological data from any period. This means, for instance, that this system can be used to predict biogenic emissions in the future. This aspect of our work is significant given the changes that biogenic organic compounds are expected to undergo as a result of changes in their climatic factors. [ABSTRACT FROM AUTHOR]

This paper presents an extensive experimental investigation on fatigue properties of carbon‐black filled isoprene rubber under complex loadings. A basic life prediction model taking strain energy density as fatigue parameter is first proposed based on fatigue crack growth tests and uniaxial tension fatigue tests under relaxing loads at room temperature. A database of fatigue life including relaxing and non‐relaxing is established through a great number of fatigue tests under five temperatures. Based on the database, two empirical parameters, that is, temperature factor (NRT/NHT) and life reinforcement factor (Re), are introduced to quantitatively characterize the coupling effects of high temperature and non‐relaxing loads on fatigue life. The fatigue mechanisms under different conditions are compared via wide‐angle x‐ray diffraction tests and postmortem analysis. It reveals that the weakening of life reinforcement at high temperatures is closely related to the strain induced crystallization behavior of rubber. [ABSTRACT FROM AUTHOR]

Volatile organic compounds (VOCs) emitted by plants may help in understanding the status of a plant's physiology and its coping with mild to severe stress. Future climatic projections reveal that shifts in temperature and CO2 availability will occur, and plants may incur the uncoupling of carbon assimilation and synthesis of key molecules. This study explores the patterns of emissions of key VOCs (isoprene, methanol, acetaldehyde, and acetic acid) emitted by poplar leaves (more than 350) under a combined gradient of temperature (12–42 °C) and air CO2 concentration (400–1500 ppm), along with measurements of photosynthetic rates and stomatal conductance. Isoprene emission exhibited a rise with temperature and CO2 availability, peaking at 39 °C, the temperature at which methanol emission started to peak, illustrating the limit of stress tolerance to severe damage. Isoprene emission was uncoupled from the photosynthesis rate, indicating a shift from the carbon source for isoprene synthesis, while assimilation was decreased. Methanol and acetaldehyde emissions were correlated with stomatal conductance and peaked at 25 °C and 1200 ppm CO2. Acetic acid emissions lacked a clear correlation with stomatal conductance and the emission pattern of its precursor acetaldehyde. This study offers crucial insights into the limitations of photosynthetic carbon and stress tolerance. [ABSTRACT FROM AUTHOR]

Many plants, especially trees, emit isoprene in a highly light‐ and temperature‐dependent manner. The advantages for plants that emit, if any, have been difficult to determine. Direct effects on membranes have been disproven. New insights have been obtained by RNA sequencing, proteomic and metabolomic studies. We determined the responses of the phosphoproteome to exposure of Arabidopsis leaves to isoprene in the gas phase for either 1 or 5 h. Isoprene effects that were not apparent from RNA sequencing and other methods but were apparent in the phosphoproteome include effects on chloroplast movement proteins and membrane remodelling proteins. Several receptor kinases were found to have altered phosphorylation levels. To test whether potential isoprene receptors could be identified, we used molecular dynamics simulations to test for proteins that might have strong binding to isoprene and, therefore might act as receptors. Although many Arabidopsis proteins were found to have slightly higher binding affinities than a reference set of Homo sapiens proteins, no specific receptor kinase was found to have a very high binding affinity. The changes in chloroplast movement, photosynthesis capacity and so forth, found in this work, are consistent with isoprene responses being especially useful in the upper canopy of trees. Summary statement: This study shows that isoprene affects the phosphoproteome important for stress tolerance. Functions such as: chloroplast movement, membrane remodelling, and stress granule formation were revealed. The study also found a signalling pathway mediated by MAP3K epsilon protein kinase 1, but no candidate receptor was found. [ABSTRACT FROM AUTHOR]

To evaluate the explosion hazard of hybrid isoprene/biogas in a primary forest environment, a 20 L spherical explosion vessel combining with a colorimetric thermometry was used to study the explosion parameters, flame structures and temperature distributions of hybrid isoprene/methane at different methane content and initial temperatures. Furthermore, the relationships between the explosion gas products and explosibility of hybrid isoprene/methane were analyzed. Experimental results showed that when the mass concentration of isoprene was 272.4 g m−3, the explosion pressure, the pressure rising rate, and the average combustion temperature reached their peak values of 0.89 MPa, 63.9 MPa s−1 and 2216 K, respectively. When the mass concentration was fixed at 272.4 g m−3, the explosibility of hybrid isoprene/methane initially enhanced and then decreased with the increasing methane volume fraction, and got the maximum values at 5 vol% methane. It was worth noting that the explosibility of hybrid methane/isoprene weakened continuously as the initial temperature increased, and it exhibited a stronger explosion power at a lower temperature. The research results would be helpful for understanding the deflagration processes and mechanisms of bush fires under various conditions, providing scientific basis for the formulation of its prevention and control measures.

Isoprenoid metabolism and its derivatives took part in photosynthesis, growth regulation, signal transduction, and plant defense to biotic and abiotic stresses. However, how aluminum (Al) stress affects the isoprenoid metabolism and whether isoprenoid metabolism plays a vital role in the Citrus plants in coping with Al stress remain unclear. In this study, we reported that Al–treatment–induced alternation in the volatilization rate of monoterpenes (α–pinene, β–pinene, limonene, α–terpinene, γ–terpinene and 3–carene) and isoprene were different between Citrus sinensis (Al-tolerant) and C. grandis (Al-sensitive) leaves. The Al-induced decrease of CO2 assimilation, maximum quantum yield of primary PSII photochemistry (Fv/Fm), the lower contents of glucose and starch, and the lowered activities of enzymes involved in the mevalonic acid (MVA) pathway and 2-C-methyl-D-erythritol 4-phosphate (MEP) pathway might account for the different volatilization rate of isoprenoids. Furthermore, the altered transcript levels of genes related to isoprenoid precursors and/or derivatives metabolism, such as geranyl diphosphate (GPP) synthase (GPPS) in GPP biosynthesis, geranylgeranyl diphosphate synthase (GGPPS), chlorophyll synthase (CHS) and GGPP reductase (GGPPR) in chlorophyll biosynthesis, limonene synthase (LS) and α-pinene synthase (APS) in limonene and α–pinene synthesis, respectively, might be responsible for the different contents of corresponding products in C. grandis and C. sinensis. Our data suggested that isoprenoid metabolism was involved in Al tolerance response in Citrus, and the alternation of some branches of isoprenoid metabolism could confer different Al-tolerance to Citrus species.

We introduce two new drought stress algorithms designed to simulate isoprene emission with the Model of Emissions of Gases and Aerosols from Nature (MEGAN) model. The two approaches include the representation of the impact of drought on isoprene emission with a simple empirical approach for offline MEGAN applications and a more process-based approach for online MEGAN in Community Land Model (CLM) simulations. The two versions differ in their implementation of leaf-temperature impacts of mild drought. For the online version of MEGAN that is coupled to CLM, the impact of drought on leaf temperature is simulated directly and the calculated leaf temperature is considered for the estimation of isoprene emission. For the offline version, we apply an empirical algorithm derived from whole-canopy flux measurements for simulating the impact of drought ranging from mild to severe stage. In addition, the offline approach adopts the ratio (f PET) of actual evapotranspiration to potential evapotranspiration to quantify the severity of drought instead of using soil moisture. We applied the two algorithms in the CLM-CAM-chem (the Community Atmosphere Model with Chemistry) model to simulate the impact of drought on isoprene emission and found that drought can decrease isoprene emission globally by 11% in 2012. We further compared the formaldehyde (HCHO) vertical column density simulated by CAM-chem to satellite HCHO observations. We found that the proposed drought algorithm can improve the match with the HCHO observations during droughts, but the performance of the drought algorithm is limited by the capacity of the model to capture the severity of drought.

Isoprene is a key trace component of the atmosphere emitted by vegetation and other organisms. It is highly reactive and can impact atmospheric composition and climate by affecting the greenhouse gases ozone and methane and secondary organic aerosol formation. Marine fluxes are poorly constrained due to the paucity of long-term measurements; this in turn limits our understanding of isoprene cycling in the ocean. Here we present the analysis of isoprene concentrations in the atmosphere measured across the Southern Ocean over 4 months in the summertime. Some of the highest concentrations (>500 ppt) originated from the marginal ice zone in the Ross and Amundsen seas, indicating the marginal ice zone is a significant source of isoprene at high latitudes. Using the United Kingdom Earth System Model we show that current estimates of sea-to-air isoprene fluxes underestimate observed isoprene by a factor >20. A daytime source of isoprene is required to reconcile models with observations. The model presented here suggests such an increase in isoprene emissions would lead to >8% decrease in the hydroxyl radical in regions of the Southern Ocean, with implications for our understanding of atmospheric oxidation and composition in remote environments, often used as proxies for the pre-industrial atmosphere. High atmospheric concentrations of isoprene have been observed in the Southern Ocean. The authors investigate their potential marine sources and show how these emissions impact the modelling of atmospheric processes and composition in remote environments. [ABSTRACT FROM AUTHOR]

One of the most concerning global environmental issues is the pollution of agricultural soils by heavy metals (HMs), especially cadmium, which not only affects human health through Cd-containing foods but also impacts the quality of rice. The soil's nitrification and denitrification processes, coupled with the release of volatile organic compounds by plants, raise substantial concerns. In this review, we summarize the recent literature related to the deleterious effects of Cd on both soil processes related to the N cycle and rice quality, particularly aroma, in different water management practices. Under both continuous flooding (CF) and alternate wetting and drying (AWD) conditions, cadmium has been observed to reduce both the nitrification and denitrification processes. The adverse effects are more pronounced in alternate wetting and drying (AWD) as compared to continuous flooding (CF). Similarly, the alteration in rice aroma is more significant in AWD than in CF. The precise modulation of volatile organic compounds (VOCs) by Cd remains unclear based on the available literature. Nevertheless, HM accumulation is higher in AWD conditions compared to CF, leading to a detrimental impact on volatile organic compounds (VOCs). The literature concludes that AWD practices should be avoided in Cd-contaminated fields to decrease accumulation and maintain the quality of the rice. In the future, rhizospheric engineering and plant biotechnology can be used to decrease the transport of HMs from the soil to the plant's edible parts. [ABSTRACT FROM AUTHOR]

A family of pyridine–oxazoline-ligated cobalt complexes L2CoCl2 3a–h were synthesized and characterized. Determined via single-crystal X-ray diffraction, complexes 3a and 3d, ligated by two ligands, displayed a distorted tetrahedral coordination of a cobalt center. The X-ray structure indicated the pyridine–oxazoline ligands acted as unusual mono-dentate ligands by coordinating only to Noxazoline. Upon activation with AlEt2Cl (diethylaluminum chloride), these cobalt complexes all exhibited high catalytic activity (up to 2.5 × 106 g·molCo−1·h−1), affording cis-1,4-co-3,4-polyisoprene with molecular weights of 4.4–176 kg mol−1 and a narrow Ð of 1.79–3.42, suggesting a single-site nature of the active sites. The structure of cobalt catalysts and reaction parameters, especially co-catalysts and the reaction temperature, all have significant influence on the polymerization activity but not on the microstructure of polyisoprene. [ABSTRACT FROM AUTHOR]

Isoprene, a lipophilic and unstable compound with the chemical formula C5H8, is transported to plant chloroplasts via the 2-C-methyl-d-erythritol 4-phosphate (MEP) pathway, which relies on photosynthesis. Although only about 20% of terrestrial plants can synthesize isoprene, those that emit it are more adaptable to oxidative and thermal stresses. To shed light on the still-elusive protective mechanism of isoprene, numerous investigations have been conducted. Isoprene has been shown to react with and quench various reactive oxygen species (ROS) such as singlet oxygen (1O2). Its reduced state and conjugated double bonds suggest that it functions as an antioxidant, although this has yet to be conclusively proven. Despite its low abundance relative to other molecules in plant tissues, recent research has explored several potential roles for isoprene including acting as a scavenger of ROS by serving as an antioxidant; strengthening cell membranes; modulating genomic, proteomic and metabolomic profiles; signaling stress responses among neighboring plants compared with other volatile organic compounds (VOCs); regulating metabolic fluxes of hormones produced through the MEP pathway; or even functioning as a free developmental hormone. Future prospective studies, such as identifying the specific receptors for VOCs along with transcription factors (TFs) and other regulatory proteins participating in the signaling pathways and also metabolomic, transcriptomic and physiological analyses could help in comprehending VOC-induced defense responses in plants under stress conditions. [ABSTRACT FROM AUTHOR]

The biosynthesis of isoprene offers a more sustainable alternative to fossil fuel-based approaches, yet its success has been largely limited to pure organic compounds and the cost remains a challenge. This study proposes a waste-to-wealth strategy for isoprene biosynthesis utilizing genetically engineered E. coli bacteria to convert organic waste from real food wastewater. The impact of organic compounds present in wastewater on E. coli growth and isoprene production was systematically investigated. The results demonstrated that with filtration pretreatment of wastewater, isoprene yield, and production achieved 115 mg/g COD and 7.1 mg/(L·h), respectively. Moreover, even without pretreatment, isoprene yield only decreased by ∼ 24%, indicating promising scalability. Glucose, maltose, glycerol, and lactate are effective substrates for isoprene biosynthesis, whereas starch, protein, and acetate do not support E. coli growth. The optimum C/N ratio for isoprene production was found to be 8:1. Furthermore, augmenting essential nutrients in wastewater elevated the isoprene yield increased to 159 mg/g COD. The wastewater biosynthesis significantly reduced the cost (44%–53% decrease, p-value < 0.01) and CO2 emission (46%–55% decrease, p-value < 0.01) compared with both sugar fermentation and fossil fuel–based refining. This study introduced a more sustainable and economically viable approach to isoprene synthesis, offering an avenue for resource recovery from wastewater. [ABSTRACT FROM AUTHOR]

In this study, we aimed to produce isoprene, a diolefin, from a mono-olefin produced by the dehydrogenation of isopentane (iso-C5). Specifically, we attempted to isomerise 2-methyl-2-butene (2M2B), a C5 mono-olefin, followed by dehydrogenation to produce isoprene. The reaction characteristics of the Fe/SiO2 catalysts were investigated in detail. In the presence of hydrogen sulphide (H2S), 2M2B was converted to 2-methyl-1-butene (2M1B) and the target product, isoprene. However, in the absence of H2S, only the isomerisation reaction proceeded, producing 2M1B; isoprene was not produced. Notably, the isoprene yield remained almost unchanged when the concentration of H2S decreased. Furthermore, when isoprene was produced by mixing iso-C5 and mono-olefins (2M2B and 2M1B), the amount of isoprene produced was significantly higher than that from iso-C5 alone. These results indicate that our synthetic strategy is promising for isoprene production. [ABSTRACT FROM AUTHOR]

The incorporation of cis‐1,4 and 3,4(+1,2) units is important to the overall properties of polyisoprene. Nevertheless, polymerization to prepare such polymer via coordinative‐insertion method has less reported. In the present study, 2,6‐bis(1H'‐allyl‐benzimidazolyl)pyridine has been installed onto the iron and cobalt prior to heterogeneous supporting. They are shown to be amenable to homogeneous polymerization of isoprene, affording 3,4(+1,2) units enriched polymer. The addition of disulfide carbon into cobalt catalyst is decisive for boosting productivity and elevating 3,4 (+1,2) insertion. Whereas, diethylphosphite external donor merely behaves as a chain transfer agent in iron catalyzed polymerization. The produced polymer with a controlled 3,4(+1,2) ratio and molar mass may find application as a single rubber, in polymer blends, composites, adhesives, and as a versatile platform for transforming to a wide range of functional polymer. Highlights: Novel iron and cobalt complexes are made.High activities toward isoprene polymerization are achieved.3,4(+1,2) incorporated polyisoprene is obtained. [ABSTRACT FROM AUTHOR]

Warming climate in the Arctic is leading to an increase in isoprene emission from ecosystems. We assessed the influence of temperature on isoprene emission from Arctic willows with laboratory and field measurements. Our findings indicate that the hourly temperature response curve of Salix spp., the dominant isoprene emitting shrub in the Arctic, aligns with that of temperate plants. In contrast, the isoprene capacity of willows exhibited a more substantial than expected response to the mean ambient temperature of the previous day, which is much stronger than the daily temperature response predicted by the current version of the Model of Emissions of Gases and Aerosols from Nature (MEGAN). With a modified algorithm from this study, MEGAN predicts 66% higher isoprene emissions for Arctic willows during an Arctic heatwave. However, despite these findings, we are still unable to fully explain the high temperature sensitivity of isoprene emissions from high latitude ecosystems. Plain Language Summary: Isoprene plays an important role in atmospheric chemistry and climate. As the climate warms, ecosystems release more isoprene into the air due to higher temperatures and changes in plant species composition. The Arctic is a hotspot for climate change. In this study, we investigated how temperature affects isoprene emissions from Arctic willow shrubs by conducting experiments in both the lab and the field. Our results show that the response of Salix spp. (willows) in the Arctic react to short‐term temperature changes is similar to plants in temperate regions. Interestingly, the amount of isoprene that willows release responds strongly to the average temperature of the previous day. This response is much stronger than predicted by models. Considering the insights from our study, isoprene emissions from Arctic willows are much higher during Arctic heatwaves than previously thought. This study can help us understand how isoprene from Arctic willows will affect atmospheric composition and climate and contribute to corresponding feedbacks on the local climate. Key Points: The hourly temperature response curve of Arctic Salix spp. is similar to temperate plants and is well represented by the Model of Emissions of Gases and Aerosols from Nature (MEGAN) modelThe isoprene capacity of willows exhibited a pronounced response to the mean temperature of the previous dayMEGAN predicts a 66% higher isoprene emission for Arctic willows during an Arctic heatwave after incorporating the findings of this study [ABSTRACT FROM AUTHOR]

Proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS) is a technique commonly used to measure ambient volatile organic compounds (VOCs) in urban, rural, and remote environments. PTR-ToF-MS is known to produce artifacts from ion fragmentation, which complicates the interpretation and quantification of key atmospheric VOCs. This study evaluates the extent to which fragmentation and other ionization processes impact urban measurements of the PTR-ToF-MS ions typically assigned to isoprene (m/z 69, C 5 H 8 H +), acetaldehyde (m/z 45, CH 3 CHO +), and benzene (m/z 79, C 6 H 6 H +). Interferences from fragmentation are identified using gas chromatography (GC) pre-separation, and the impact of these interferences is quantified using ground-based and airborne measurements in a number of US cities, including Las Vegas, Los Angeles, New York City, and Detroit. In urban regions with low biogenic isoprene emissions (e.g., Las Vegas), fragmentation from higher-carbon aldehydes and cycloalkanes emitted from anthropogenic sources may contribute to m/z 69 by as much as 50 % during the day, while the majority of the signal at m/z 69 is attributed to fragmentation during the night. Interferences are a higher fraction of m/z 69 during airborne studies, which likely results from differences in the reactivity between isoprene and the interfering species along with the subsequent changes to the VOC mixture at higher altitudes. For other PTR masses, including m/z 45 and m/z 79, interferences are observed due to fragmentation and O 2+ ionization of VOCs typically used in solvents, which are becoming a more important source of anthropogenic VOCs in urban areas. We present methods to correct these interferences, which provide better agreement with GC measurements of isomer-specific molecules. These observations show the utility of deploying GC pre-separation for the interpretation PTR-ToF-MS spectra. [ABSTRACT FROM AUTHOR]

The most widely used isoprene emission algorithm, G93 formula, estimates instantaneous leaf-level isoprene emission using the basal emission factor and light and temperature dependency parameters. The G93 parameters have been suggested to show variation depending on past weather conditions, but no study has closely examined the relationship between past meteorological data and the algorithm parameters. Here, to examine the influence of the past weather on these parameters, we monitored weather conditions, G93 parameters, isoprene synthase transcripts and protein levels, and MEP pathway metabolites in the tropical tree Ficus septica for 12 days and analyzed their relationship with cumulative temperature and light intensity. Plants were illuminated with varying (ascending and descending) light regimes, and our previously developed Ping-Pong optimization method was used to parameterize G93. The cumulative temperature of the past 5 and 7 days positively correlated with CT2 and α, respectively, while the cumulative light intensity of the past 10 days showed the highest negative correlation with α. Concentrations of MEP pathway metabolites and IspS gene expression increased with increasing cumulative temperature. At best, the cumulative temperature of the past 2 days positively correlated with the MEP pathway metabolites and IspS gene expression, while these factors showed a biphasic positive and negative correlation with cumulative light intensity. Optimized G93 captured well the temperature and light dependency of isoprene emission at the beginning of the experiment; however, its performance significantly decreased for the latter stages of the experimental duration, especially for the descending phase. This was successfully improved through separate optimization of the ascending and descending phases, emphasizing the importance of the optimization of formula parameters and model improvement. These results have important implications for the improvement of isoprene emission algorithms, particularly under the predicted increase in future global temperatures. [ABSTRACT FROM AUTHOR]

In this study, a series of structurally rigid cyclooctyl-fused iminopyridine iron complexes, [L2FeCl][FeCl4] and [2L3Fe][Cl][3FeCl4], was synthesized via a one-pot method and investigated as precatalysts in conjunction with methylaluminoxane for isoprene (Ip) polymerization. Combined characterization through FTIR analysis, elemental analysis and single crystal XRD analysis fully verified the structure of these complexes. The most active iron complex, FeH, exhibited a trisligated nature, with its cation adopting an octahedral geometry around the metal center. In contrast, all the other iron complexes (Fe2Me, Fe2Et, Fe2iPr, Fe3Me, Fe2Et,Me) displayed bisligated configurations, with distorted trigonal bipyramidal geometry of cations. During isoprene polymerization, the extent of steric hindrance of the ligand framework exerted a significant impact on catalytic performance. The FeH precatalyst with less steric hindrance demonstrated excellent performance, producing high molecular weight polyisoprenes with conversions exceeding 99% for 4000 equiv. of monomer. Even at very low catalyst loadings, as low as 0.0025 mol% (Fe/Ip), the polymerization of isoprene could proceed smoothly with an exceptionally high activity of 4.0 × 106 gPI (molFe, h)−1. Moreover, this precatalyst exhibited good thermal stability, maintaining high activity levels (typically 105 gPI (molFe, h)−1) across a broad temperature range from −20 °C to 100 °C. Additionally, by adjusting steric substituents and the reaction temperature, the 1,4/3,4 regioselectivity could be modulated from 9/91 to 69/31 while maintaining a high stereoselectivity of cis-1,4 structures (cis/trans: >99/1). [ABSTRACT FROM AUTHOR]

Climate change profoundly affects the timing of seasonal activities of organisms, known as phenology. The impact of climate change is not unidirectional; it is also influenced by plant phenology as plants modify atmospheric composition and climatic processes. One important aspect of this interaction is the emission of biogenic volatile organic compounds (BVOCs), which link the Earth's surface, atmosphere, and climate. BVOC emissions exhibit significant diurnal and seasonal variations and are therefore considered essential phenological traits. To understand the dynamic equilibrium arising from the interplay between plant phenology and climate, this review presents recent advances in comprehending the molecular mechanisms underpinning plant phenology and its interaction with climate. We provide an overview of studies investigating molecular phenology, genome-wide gene expression analyses conducted in natural environments, and how these studies revolutionize the concept of phenology, shifting it from observable traits to dynamic molecular responses driven by gene–environment interactions. We explain how this knowledge can be scaled up to encompass plant populations, regions, and even the globe by establishing connections between molecular phenology, changes in plant distribution, species composition, and climate. [ABSTRACT FROM AUTHOR]

Abstract Accurately measuring emission factors (Es) of biogenic volatile organic compounds (BVOCs) with consideration of intraspecific variability is vital but often overlooked. This study presents in‐situ measurements of BVOC emissions from 114 Eucalyptus urophylla individuals using the LI‐6800 portable photosynthesis system. We observed intraspecific variability exceeding an order of magnitude in BVOC Es. Despite this variability, our approach yielded statistically representative Es for E. urophylla, yet challenging the feasibility of extensive field measurements. By quickly screening net photosynthesis rate (Pn) across a broad set of individuals and selecting those within a specific Pn range, such as mean ± 0.1 × SD (standard deviation) of Pn for all screened individuals, for detailed BVOC emission measurements, we achieved comparable mean Es with approximately 10% of the original sampling effort. This offers a practical solution for efficient and accurate field measurement of representative BVOC Es, significantly reducing required sample size while effectively addressing intraspecific variability.

High molar mass copolymers with a tapered interface are mechanically tough materials with an accessible order-to-disorder transition temperature and hence processability. We report the first ordering kinetics for a tapered tetrablock copolymer in comparison to a conventional diblock copolymer made sequentially. We show that tapered copolymers belong to the Brazovskii "universality class," where fluctuations play a dominant role. Consequently, the order-to-disorder transition has a very weak, fluctuation-induced first-order character. The ordering kinetics of the lamellar phase from the supercooled disordered melt revealed several distinct differences associated with the range of metastability (increased), the timescales (bimodal), and the exact mechanism of ordering. The results are discussed in terms of the reduced interaction parameter and the introduction of structural defects within the lamellar grains. [ABSTRACT FROM AUTHOR]

A combination of electrospray ionization, matrix-assisted laser desorption/ionization and gas chromatography–mass-spectrometry (GC–MS) with electron ionization is used for the analysis of products and intermediates of the isoprene telomerization reaction catalyzed by N-heterocyclic carbene Pd(II) complexes in presence of methanol. It is shown that soft ionization mass spectrometry techniques allow the detection of the main catalytically active cationic intermediate of palladium in real time whereas GC–MS is efficient in the structure determination of hydrogenated telomerization products. The data obtained are confirmed by NMR spectrometry. [ABSTRACT FROM AUTHOR]

Several cobalt(II) complexes Co1–Co3 bearing pyridine–oxime ligands (L1 = pyridine-2-aldoxime for Co1; L2 = 6-methylpyridine-2-aldoxime for Co2; L3 = phenyl-2-pyridylketoxime for Co3) and picolinaldehyde O-methyl oxime (L4)-supported Co4 were synthesized and well characterized by FT-IR, mass spectrum and elemental analysis. The single-crystal X-ray diffraction of complex Co2 reveals that the cobalt center of CoCl2 is coordinated with two 6-methylpyridine-2-aldoxime ligands binding with Npyridine and Noxime atoms, which feature a distorted octahedral structure. These Co complexes Co1–Co4 displayed extremely high activity toward isoprene polymerization upon activation with small amount of AlClEt2 in toluene, giving polyisoprene with high activity up to 16.3 × 105 (mol of Co)−1(h)−1. And, the generated polyisoprene displayed high molecular weights and narrow molecular distribution with a cis-1,4-enriched selectivity. The type of cobalt complexes, cocatalyst and reaction temperature all have effects on the polymerization activity but not on the microstructure of polymer. [ABSTRACT FROM AUTHOR]

Isoprene is a crucial non-methane biogenic volatile organic compound (BVOC) that exhibits the largest emissions globally. It is chemically reactive in the atmosphere and serves as the primary source of generating secondary organic aerosols (SOA) in terrestrial and remote marine regions. However, a comprehensive estimation of marine isoprene emissions is currently lacking. Here we built a module to present a 20-year (2001–2020) global hourly dataset for marine isoprene emissions, including phytoplankton-generated biological emissions (BIO emissions) and photochemistry-generated emissions in the sea surface microlayer (SML emissions) based on the latest advancements in biological, physical, and chemical processes, with high spatial resolutions. Our dataset suggests the annual global marine isoprene emissions amount to 1.097±0.009 Tg yr -1. Among these, the BIO emissions are 0.481±0.008 Tg yr -1 while SML emissions contribute 0.616±0.003 Tg yr -1. The ability of this module to estimate marine isoprene emissions was evaluated through comparison with a series of observations of marine isoprene concentrations and emission fluxes. The annual total isoprene emissions across the tropical ocean show a declining trend from 2001 to 2020. Most ocean regions exhibit a 1-year emission period, whereas a significant intraseasonal period is found in the tropical ocean. This dataset can be employed as input for the simulation of marine SOA formation in earth system models. This work provides the foundation for further studies into the impact of the air–sea system on marine SOA formation and its climate effect. The DOI link for the dataset is 10.11888/Atmos.tpdc.300521 (Cui and Zhu, 2023). [ABSTRACT FROM AUTHOR]

Co‐oxidation of a range of alkenes, dienes, and aromatic compounds by whole cells of the isoprene‐degrading bacterium Rhodococcus sp. AD45 expressing isoprene monooxygenase was investigated, revealing a relatively broad substrate specificity for this soluble diiron centre monooxygenase. A range of 1‐alkynes (C2–C8) were tested as potential inhibitors. Acetylene, a potent inhibitor of the related enzyme soluble methane monooxygenase, had little inhibitory effect, whereas 1‐octyne was a potent inhibitor of isoprene monooxygenase, indicating that 1‐octyne could potentially be used as a specific inhibitor to differentiate between isoprene consumption by bona fide isoprene degraders and co‐oxidation of isoprene by other oxygenase‐containing bacteria, such as methanotrophs, in environmental samples. The isoprene oxidation kinetics of a variety of monooxygenase‐expressing bacteria were also investigated, revealing that alkene monooxygenase from Xanthobacter and soluble methane monooxygenases from Methylococcus and Methylocella, but not particulate methane monooxygenases from Methylococcus or Methylomicrobium, could co‐oxidise isoprene at appreciable rates. Interestingly the ammonia monooxygenase from the nitrifier Nitrosomonas europaea could also co‐oxidise isoprene at relatively high rates, suggesting that co‐oxidation of isoprene by additional groups of bacteria, under the right conditions, might occur in the environment. [ABSTRACT FROM AUTHOR]

In recent years, anthropogenic activities and climate change have significantly increased exposure of plants to environmental stresses (single or multiple) and pollutants, which negatively affect plant growth, survival, and productivity. Plants may activate an armament of defenses against such environmental stresses. Isoprene, the most abundant biogenic volatile organic compound emitted by plants, is supposed to induce stress tolerance directly, by quenching reactive oxygen species, or indirectly by strengthening photosynthetic membranes and reprogramming expression of genes that are involved in antioxidant defense mechanisms. On the other hand, isoprene is also involved in tropospheric chemistry that contributes to the production of air pollutants when mixing with anthropogenic gases. In this review, we summarized current knowledge about the impact of air and soil pollutants on isoprene emission from plants, focusing on possible feedback and feedforward mechanisms that may affect whole ecosystem functioning and evolution of plant species. Despite limited available information, especially about long-term effects of soil pollutants, it may be speculated that isoprene generally improves fitness of plants challenged by air and soil pollutants, and their interaction with other organisms. [ABSTRACT FROM AUTHOR]