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1.
Sci Total Environ ; 926: 171928, 2024 May 20.
Artigo em Inglês | MEDLINE | ID: mdl-38531457

RESUMO

Styrene butadiene rubber is one of the main constituents of tire tread. During tire life, the tread material undergoes different stresses that impact its structure and chemical composition. Wear particles are then released into the environment as weathered material. To understand their fate, it is important to start with a better characterization of abiotic and biotic degradation of the elastomer material. A multi-disciplinary approach was implemented to study the photo- and thermo- degradation of non-vulcanized SBR films containing 15 w% styrene as well as their potential biodegradation by Rhodoccocus ruber and Gordonia polyisoprenivorans bacterial strains. Each ageing process leads to crosslinking reactions, much surface oxidation of the films and the production of hundreds of short chain compounds. These degradation products present a high level of unsaturation and oxidation and can be released into water to become potential substrates for microorganisms. Both strains were able to degrade from 0.2 to 1.2 % (% ThOD) of the aged SBR film after 30-day incubation while no biodegradation was observed on the pristine material. A 25-75 % decrease in the signal intensity of water extractable compounds was observed, suggesting that biomass production was linked to the consumption of low-molecular-weight degradation products. These results evidence the positive impact of abiotic degradation on the biodegradation process of styrene butadiene rubber.


Assuntos
Butadienos , Elastômeros , Borracha , Estirenos , Estireno , Água
2.
Anal Chim Acta ; 1301: 342468, 2024 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-38553125

RESUMO

BACKGROUND: Acetone, isoprene, and other volatile organic compounds (VOCs) in exhaled breath have been shown to be biomarkers for many medical conditions. Researchers use different techniques for VOC detection, including solid phase microextraction (SPME), to preconcentrate volatile analytes prior to instrumental analysis by gas chromatography-mass spectrometry (GC-MS). These techniques include a previously developed method to detect VOCs in breath directly using SPME, but it is uncommon for studies to quantify exhaled volatiles because it can be time consuming due to the need of many external/internal standards, and there is no standardized or widely accepted method. The objective of this study was to develop an accessible method to quantify acetone and isoprene in breath by SPME GC-MS. RESULTS: A system was developed to mimic human exhalation and expose VOCs to a SPME fiber in the gas phase at known concentrations. VOCs were bubbled/diluted with dry air at a fixed flow rate, duration, and volume that was comparable to a previously developed breath sampling method. Identification of acetone and isoprene through GC-MS was verified using standards and observing overlaps in chromatographic retention/mass spectral fragmentation. Calibration curves were developed for these two analytes, which showed a high degree of linear correlation. Acetone and isoprene displayed limits of detection/quantification equal to 12 ppb/37 ppb and 73 ppb/222 ppb respectively. Quantification results in healthy breath samples (n = 15) showed acetone concentrations spanned between 71 ppb and 294 ppb, and isoprene varied between 170 ppb and 990 ppb. Both concentration ranges for acetone and isoprene in this study overlap with those reported in existing literature. SIGNIFICANCE: Results indicate the development of a system to quantify acetone and isoprene in breath that can be adapted to diverse sampling methods and instrumental analyses beyond SPME GC-MS.


Assuntos
Butadienos , Hemiterpenos , Microextração em Fase Sólida , Compostos Orgânicos Voláteis , Humanos , Cromatografia Gasosa-Espectrometria de Massas/métodos , Microextração em Fase Sólida/métodos , Acetona/análise , Expiração , Testes Respiratórios/métodos , Compostos Orgânicos Voláteis/análise
3.
ACS Sens ; 9(3): 1575-1583, 2024 Mar 22.
Artigo em Inglês | MEDLINE | ID: mdl-38483350

RESUMO

Monitoring of isoprene in exhaled breath is expected to provide a noninvasive and painless method for dynamic monitoring of physiological and metabolic states during exercise. However, for real-time and portable detection of isoprene, gas sensors have become the best choice for gas detection technology, which are crucial to achieving the goal of anytime, anywhere, human-centered healthcare in the future. Here, we first report a mixed potential type isoprene sensor based on a Gd2Zr2O7 solid electrolyte and a CdSb2O6 sensing electrode, which enables sensitive detection for isoprene with sensitivities of -21.2 mV/ppm and -65.8 mV/decade in the range of 0.05-1 and 1-100 ppm. The sensing behavior of the sensor follows the mixed potential sensing mechanism and was further verified by the electrochemical polarization curves. The significant differentiation between the sensor response to exhaled breath of healthy individuals and simulated breath containing different concentrations of isoprene demonstrates the potential of the sensor for the detection of isoprene in exhaled breath. Simultaneously, monitoring of isoprene during exercise signifies the feasibility of the sensor in dynamic monitoring of physiological indicators, which is not only of great significance for optimizing training and guiding therapeutic exercise intervention in sporting scenarios but also expected to help further reveal the interaction between exercise, muscle, and organ metabolism in medicine.


Assuntos
Testes Respiratórios , Gases , Hemiterpenos , Humanos , Testes Respiratórios/métodos , Butadienos , Biomarcadores
4.
J Cell Mol Med ; 28(8): 1-11, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38526036

RESUMO

Dysregulated angiogenesis leads to neovascularization, which can promote or exacerbate various diseases. Previous studies have proved that NEDD4L plays an important role in hypertension and atherosclerosis. Hence, we hypothesized that NEDD4L may be a critical regulator of endothelial cell (EC) function. This study aimed to define the role of NEDD4L in regulating EC angiogenesis and elucidate their underlying mechanisms. Loss- and gain-of-function of NEDD4L detected the angiogenesis and mobility role in human umbilical vein endothelial cells (HUVECs) using Matrigel tube formation assay, cell proliferation and migration. Pharmacological pathway inhibitors and western blot were used to determine the underlying mechanism of NEDD4L-regulated endothelial functions. Knockdown of NEDD4L suppressed tube formation, cell proliferation and cell migration in HUVECs, whereas NEDD4L overexpression promoted these functions. Moreover, NEDD4L-regulated angiogenesis and cell progression are associated with the phosphorylation of Akt, Erk1/2 and eNOS and the expression of VEGFR2 and cyclin D1 and D3. Mechanically, further evidence was confirmed by using Akt blocker MK-2206, Erk1/2 blocker U0126 and eNOS blocker L-NAME. Overexpression NEDD4L-promoted angiogenesis, cell migration and cell proliferation were restrained by these inhibitors. In addition, overexpression NEDD4L-promoted cell cycle-related proteins cyclin D1 and D3 were also suppressed by Akt blocker MK-2206, Erk1/2 blocker U0126 and eNOS blocker L-NAME. Our results demonstrated a novel finding that NEDD4L promotes angiogenesis and cell progression by regulating the Akt/Erk/eNOS pathways.


Assuntos
Butadienos , Ciclina D1 , Nitrilas , Transdução de Sinais , Humanos , Células Endoteliais da Veia Umbilical Humana/metabolismo , Ciclina D1/metabolismo , Proteínas Proto-Oncogênicas c-akt/metabolismo , NG-Nitroarginina Metil Éster , 60489 , Neovascularização Fisiológica/genética , Proliferação de Células , Movimento Celular/genética
5.
Chem Res Toxicol ; 37(2): 374-384, 2024 02 19.
Artigo em Inglês | MEDLINE | ID: mdl-38315500

RESUMO

Approximately 10% of smokers will develop lung cancer. Sensitive predictive biomarkers are needed to identify susceptible individuals. 1,3-Butadiene (BD) is among the most abundant tobacco smoke carcinogens. BD is metabolically activated to 3,4-epoxy-1-butene (EB), which is detoxified via the glutathione conjugation/mercapturic acid pathway to form monohydroxybutenyl mercapturic acid (MHBMA) and dihydroxybutyl mercapturic acid (DHBMA). Alternatively, EB can react with guanine nucleobases of DNA to form N7-(1-hydroxyl-3-buten-1-yl) guanine (EB-GII) adducts. We employed isotope dilution LC/ESI-HRMS/MS methodologies to quantify MHBMA, DHBMA, and EB-GII in urine of smokers who developed lung cancer (N = 260) and matched smoking controls (N = 259) from the Southern Community Cohort (white and African American). The concentrations of all three biomarkers were significantly higher in smokers that subsequently developed lung cancer as compared to matched smoker controls after adjusting for age, sex, and race/ethnicity (p < 0.0001 for EB-GII, p < 0.0001 for MHBMA, and p = 0.0007 for DHBMA). The odds ratio (OR) for lung cancer development was 1.63 for MHBMA, 1.37 for DHBMA, and 1.97 for EB-GII, with a higher OR in African American subjects than in whites. The association of urinary EB-GII, MHBMA, and DHBMA with lung cancer status did not remain upon adjustment for total nicotine equivalents. These findings reveal that urinary MHBMA, DHBMA, and EB-GII are directly correlated with the BD dose delivered via smoking and are associated with lung cancer risk.


Assuntos
Neoplasias Pulmonares , Produtos do Tabaco , Humanos , Fumantes , Butadienos/metabolismo , Acetilcisteína/metabolismo , Neoplasias Pulmonares/induzido quimicamente , Guanina , Biomarcadores/urina , Adutos de DNA
6.
Ecotoxicol Environ Saf ; 272: 116037, 2024 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-38301581

RESUMO

BACKGROUND: In the plastics production sector, bisphenol S (BPS) has gained popularity as a replacement for bisphenol A (BPA). However, the mode of action (MOA) of female reproductive toxicity caused by BPS remains unclear and the safety of BPS is controversial. METHODS: Human normal ovarian epithelial cell line, IOSE80, were exposed to BPS at human-relevant levels for short-term exposure at 24 h or 48 h, or for long-term exposure at 28 days, either alone or together with five signaling pathway inhibitors: ICI 18,2780 (estrogen receptor [ER] antagonist), G15 (GPR30 specific inhibitor), U0126 (extracellular regulated protein kinase [ERK] 1/2 inhibitor), SP600125 (c-Jun N-terminal kinase [JNK] inhibitor) or SB203580 (p38 mitogen­activated protein kinase [p38MAPK] inhibitor). MOA through ERß-MAPK signaling pathway interruption was explored, and potential thresholds were estimated by the benchmark dose method. RESULTS: For short-term exposure, BPS exposure at human-relevant levels elevated the ESR2 and MAPK8 mRNA levels, along with the percentage of the G0/G1 phase. For long-term exposure, BPS raised the MAPK1 and EGFR mRNA levels, the ERß, p-ERK, and p-JNK protein levels, and the percentage of the G0/G1 phase, which was partly suppressed by U0126. The benchmark dose lower confidence limit (BMDL) of the percentage of the S phase after 24 h exposure was the lowest among all the BMDLs of a good fit, with BMDL5 of 9.55 µM. CONCLUSIONS: The MOA of female reproductive toxicity caused by BPS at human-relevant levels might involve: molecular initiating event (MIE)-BPS binding to ERß receptor, key event (KE)1-the interrupted expression of GnRH, KE2-the activation of JNK (for short-term exposure) and ERK pathway (for long-term exposure), KE3-cell cycle arrest (the increased percentage of the G0/G1 phase), and KE4-interruption of cell proliferation (only for short-term exposure). The BMDL of the percentage of the S phase after 24 h exposure was the lowest among all the BMDLs of a good fit, with BMDL5 of 9.55 µM.


Assuntos
Butadienos , Receptor beta de Estrogênio , Sistema de Sinalização das MAP Quinases , Nitrilas , Humanos , Feminino , Receptor beta de Estrogênio/genética , Receptor beta de Estrogênio/metabolismo , Transdução de Sinais , Células Epiteliais/metabolismo , RNA Mensageiro/metabolismo
7.
PeerJ ; 12: e16748, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38304189

RESUMO

Acute lung injury (ALI) is one of the most serious complications of sepsis, characterized by high morbidity and mortality rates. Ferroptosis has recently been reported to play an essential role in sepsis-induced ALI. Excessive neutrophil extracellular traps (NETs) formation induces exacerbated inflammation and is crucial to the development of ALI. In this study, we explored the effects of ferroptosis and NETs and observed the therapeutic function of mesenchymal stem cells (MSCs) on sepsis-induced ALI. First, we produced a cecal ligation and puncture (CLP) model of sepsis in rats. Ferrostain-1 and DNase-1 were used to inhibit ferroptosis and NETs formation separately, to confirm their effects on sepsis-induced ALI. Next, U0126 was applied to suppress the MEK/ERK signaling pathway, which is considered to be vital to NETs formation. Finally, the therapeutic effect of MSCs was observed on CLP models. The results demonstrated that both ferrostain-1 and DNase-1 application could improve sepsis-induced ALI. DNase-1 inhibited ferroptosis significantly in lung tissues, showing that ferroptosis could be regulated by NETs formation. With the inhibition of the MEK/ERK signaling pathway by U0126, NETs formation and ferroptosis in lung tissues were both reduced, and sepsis-induced ALI was improved. MSCs also had a similar protective effect against sepsis-induced ALI, not only inhibiting MEK/ERK signaling pathway-mediated NETs formation, but also alleviating ferroptosis in lung tissues. We concluded that MSCs could protect against sepsis-induced ALI by suppressing NETs formation and ferroptosis in lung tissues. In this study, we found that NETs formation and ferroptosis were both potential therapeutic targets for the treatment of sepsis-induced ALI, and provided new evidence supporting the clinical application of MSCs in sepsis-induced ALI treatment.


Assuntos
Lesão Pulmonar Aguda , Butadienos , Armadilhas Extracelulares , Ferroptose , Células-Tronco Mesenquimais , Nitrilas , Sepse , Ratos , Animais , Armadilhas Extracelulares/metabolismo , Lesão Pulmonar Aguda/etiologia , Desoxirribonuclease I/farmacologia , Sepse/complicações , Células-Tronco Mesenquimais/metabolismo , Quinases de Proteína Quinase Ativadas por Mitógeno/efeitos adversos
8.
J Chromatogr A ; 1719: 464740, 2024 Mar 29.
Artigo em Inglês | MEDLINE | ID: mdl-38401373

RESUMO

Desktop 3D printers that operate by the fused deposition modeling (FDM) mechanism are known to release numerous hazardous volatile organic compounds (VOCs) during printing, including some with potential carcinogenic effects. Operating in a similar manner to FDM 3D printers, 3D pens have gained popularity recently from their ability to allow users to effortlessly draw in the air or create various 3D printed shapes while handling the device like a pen. In contrast to numerous modern 3D printers, 3D pens lack their own ventilation systems and are often used in settings with minimum airflow. Their operation makes users more vulnerable to VOC emissions, as the released VOCs are likely to be in the breathing zone. Consequently, monitoring VOCs released during the use of 3D pens is crucial. In this study, VOCs liberated while extruding acrylonitrile butadiene styrene (ABS) filaments from a 3D pen were measured by solid-phase microextraction (SPME) combined with gas chromatography/mass spectrometry (GC/MS). SPME was investigated using the traditional fiber and Arrow geometries with the DVB/Carbon WR/PDMS sorbent while four different brands of ABS filaments-Amazon Basics, Gizmodork, Mynt 3D, and Novamaker-were used with the 3D pen. Heatmap analysis showed differentiation among these brands based on the liberated VOCs. The nozzle temperature and printing speed were found to affect the number and amount of released VOCs. This study goes a step further and presents for the first time a comparison between 3D pen and a desktop 3D printer based on liberated VOCs. Interestingly, the findings reveal that the 3D pen releases a greater number and amount of VOCs compared to the printer. The amounts of liberated VOCs, as indicated by the corresponding chromatographic peak areas, were found to be 1.4 to 62.6 times higher for the 3D pen compared to the 3D printer when using SPME Arrow.


Assuntos
Acrilonitrila , Butadienos , Compostos Orgânicos Voláteis , Compostos Orgânicos Voláteis/análise , Microextração em Fase Sólida/métodos , Impressão Tridimensional , Estireno
9.
Biofabrication ; 16(2)2024 02 09.
Artigo em Inglês | MEDLINE | ID: mdl-38331416

RESUMO

Fabrication of a biohybrid actuator requires muscle cells anisotropically aligned in a line, curve, or combination of lines and curves (similar to the microstructure of living muscle tissue) to replicate lifelike movements, in addition to considering the arrangement of skeletal structure or muscular structure with anisotropic straight patterns. Here, we report a UV laser-processed microstructure for freely directing cellular alignment to engineer a biohybrid actuator composed of poly(styrene-block-butadiene-block-styrene triblock copolymer) (SBS) thin film with tailor-made microgrooves (MGs) and skeletal myotubes aligned along these MGs. Specifically, straight, circular, or curved MGs were transferred to SBS thin films from a UV laser-processed template, allowing for the successful alignment of myotubes along MGs. The biohybrid actuator, composed of anisotropically aligned myotubes on a curved microgrooved SBS thin film, was contracted by electrical stimulation. Contraction of biohybrid actuators with curved aligned myotubes permits twisted-like behavior, unlike straight microgrooved films. Therefore, the UV laser-ablation system is a unique maskless and rapid microfabrication technique that provides intriguing opportunities for omni-directional microgrooved structures to achieve the complex motion of living organisms.


Assuntos
Butadienos , Fibras Musculares Esqueléticas , Poliestirenos , Anisotropia , Lasers
10.
J Pharmacol Sci ; 154(3): 139-147, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38395514

RESUMO

Vasoactive intestinal peptide (VIP) receptor 2 (VIPR2) is a G protein-coupled receptor that binds to Gαs, Gαi, and Gαq proteins to regulate various downstream signaling molecules, such as protein kinase A (PKA), phosphatidylinositol 3-kinase (PI3K), and phospholipase C. In this study, we examined the role of VIPR2 in cell cycle progression. KS-133, a newly developed VIPR2-selective antagonist peptide, attenuated VIP-induced cell proliferation in MCF-7 cells. The percentage of cells in the S-M phase was decreased in MCF-7 cells treated with KS-133. KS-133 in the presence of VIP decreased the phosphorylation of extracellular signal-regulated kinase (ERK), AKT, and glycogen synthase kinase-3ß (GSK3ß), resulting in a decrease in cyclin D1 levels. In MCF-7 cells stably-expressing VIPR2, KS-133 decreased PI3K activity and cAMP levels. Treatment with the ERK-specific kinase (MEK) inhibitor U0126 and the class I PI3K inhibitor ZSTK474 decreased the percentage of cells in the S phase. KS-133 reduced the percentage of cells in the S phase more than treatment with U0126 or ZSTK474 alone and did not affect the effect of the mixture of these inhibitors. Our findings suggest that VIPR2 signaling regulates cyclin D1 levels through the cAMP/PKA/ERK and PI3K/AKT/GSK3ß pathways, and mediates the G1/S transition to control cell proliferation.


Assuntos
Butadienos , Ciclina D1 , Nitrilas , Peptídeos Cíclicos , Proteínas Proto-Oncogênicas c-akt , Humanos , Ciclina D1/genética , Proteínas Proto-Oncogênicas c-akt/metabolismo , Células MCF-7 , Receptores Tipo II de Peptídeo Intestinal Vasoativo , Fosfatidilinositol 3-Quinases/metabolismo , Glicogênio Sintase Quinase 3 beta , Divisão Celular , MAP Quinases Reguladas por Sinal Extracelular/metabolismo , Proliferação de Células , Fosfatidilinositol 3-Quinase
11.
Cell Commun Signal ; 22(1): 76, 2024 01 29.
Artigo em Inglês | MEDLINE | ID: mdl-38287382

RESUMO

The crosstalk between astrocytes and microglia plays a pivotal role in neuroinflammation following ischemic stroke, and phenotypic distribution of these cells can change with the progression of ischemic stroke. Peroxiredoxin (PRDX) 6 phospholipase A2 (iPLA2) activity is involved in the generation of reactive oxygen species(ROS), with ROS driving the activation of microglia and astrocytes; however, its exact function remains unexplored. MJ33, PRDX6D140A mutation was used to block PRDX6-iPLA2 activity in vitro and vivo after ischemic stroke. PRDX6T177A mutation was used to block the phosphorylation of PRDX6 in CTX-TNA2 cell lines. NAC, GSK2795039, Mdivi-1, U0126, and SB202190 were used to block the activity of ROS, NOX2, mitochondrial fission, ERK, and P38, respectively, in CTX-TNA2 cells. In ischemic stroke, PRDX6 is mainly expressed in astrocytes and PRDX6-iPLA2 is involved in the activation of astrocytes and microglia. In co-culture system, Asp140 mutation in PRDX6 of CTX-TNA2 inhibited the polarization of microglia, reduced the production of ROS, suppressed NOX2 activation, and inhibited the Drp1-dependent mitochondrial fission following OGD/R. These effects were further strengthened by the inhibition of ROS production. In subsequent experiments, U0126 and SB202190 inhibited the phosphorylation of PRDX6 at Thr177 and reduced PRDX6-iPLA2 activity. These results suggest that PRDX6-iPLA2 plays an important role in the astrocyte-induced generation of ROS and activation of microglia, which are regulated by the activation of Nox2 and Drp1-dependent mitochondrial fission pathways. Additionally, PRDX6-iPLA2 activity is regulated by MAPKs via the phosphorylation of PRDX6 at Thr177 in astrocytes.


Assuntos
Astrócitos , Butadienos , AVC Isquêmico , Nitrilas , Humanos , Espécies Reativas de Oxigênio/metabolismo , Astrócitos/metabolismo , Microglia/metabolismo , Doenças Neuroinflamatórias , Peroxirredoxina VI/genética , Peroxirredoxina VI/metabolismo
12.
Environ Pollut ; 344: 123311, 2024 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-38195025

RESUMO

The road dust and roadside soil can act as both sinks and sources of hexachlorobutadiene (HCBD) and chlorobenzenes (CBzs), but comparative research on these two adjacent media is extremely limited. In this study, HCBD and CBzs were simultaneously analyzed in road dust and roadside soil samples from an area containing both industrial factories and residential communities in Eastern China. The road dust there was found to have 2-6 times higher contents of HCBD (mean 1.14 ng/g, maximum 6.44 ng/g) and ∑Cl3-Cl6CBzs (22.8 ng/g, 90.6 ng/g) than those in the roadside soil. The spatial distributions of HCBD and CBzs in road dusts were affected by various types of sources, showing no significant discrepancy among the sites. On the contrast, HCBD and CBzs contamination in roadside soils occurring near several factories were strongly correlated to their industrial point sources. Risk assessments showed, at current contamination levels in the road dust and roadside soil, HCBD and CBzs are not likely to induce carcinogenic or non-carcinogenic risks to residents in the studied area. Nevertheless, road dust ingestion, as the major exposure pathway of HCBD and CBzs, should be avoided to reduce the exposure risk. These findings based on the contamination differences between two media provide a new perspective and evidence for screening important sources and exposure pathway of HCBD and CBzs, which would be helpful to their source identification and risk control.


Assuntos
Butadienos , Metais Pesados , Poluentes do Solo , Solo , Monitoramento Ambiental , Clorobenzenos/análise , Poeira/análise , Poluentes do Solo/análise , China , Medição de Risco , Metais Pesados/análise , Cidades
13.
Molecules ; 29(2)2024 Jan 22.
Artigo em Inglês | MEDLINE | ID: mdl-38276620

RESUMO

The chemistry of conjugated nitrodienes is becoming increasingly popular. These molecules are successfully applied in cycloaddition to synthesize six-membered rings in Diels-Alder reactions. Nitrodienes can be also applied to obtain bis-compounds in [3+2] cycloaddition. Moreover, the presence of a nitro group in the structure provides a possibility of further modification of the products. The simplest symmetrical representative of conjugated nitrodienes is (1E,3E)-1,4-dinitro-1,3-butadiene. Although the first mentions of the compound date back to the early 1950s, the compound has not yet been examined thoroughly enough. Therefore, in this article, a comprehensive study of (1E,3E)-1,4-dinitro-1,3-butadiene has been described. For this purpose, an experimental study including the synthesis process as well as an evaluation of the spectral characteristics has been conducted. So as to better understand the properties of this compound, a computational study of reactivity indices based on MEDT and also an assessment of pharmacokinetics and biological activity according to ADME and PASS methodologies have been made. On this basis, some future application trends of (1E,3E)-1,4-dinitro-1,3-butadiene have been proposed.


Assuntos
Butadienos , Butadienos/química , Simulação por Computador
14.
Macromol Rapid Commun ; 45(7): e2300653, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38261808

RESUMO

Herein, a concise, effective, and scalable strategy is reported that the introduction of polar molecules (PMs) (e.g., anisole (PhOMe), phenetole (PhOEt), 2-methoxynaphthalene (NaphOMe), thioanisole (PhSMe), and N,N-dimethylaniline (PhNMe2)) as continuously coordinated neutral ligand of cationic active species in situ generated from the constrain-geometry-configuration-type rare-earth metal complexes A-F/AliBu3/[Ph3C][B(C6F5)4] ternary systems can easily switch the regio- and stereoselectivity of the polymerization of conjugated dienes (CDs, including 2-subsituted CDs such as isoprene (IP) and myrcene (MY), 1,2-disubstituted CD ocimene (OC), and 1-substituted polar CD 1-(para-methoxyphenyl)-1,3-butadiene (p-MOPB)) from poor selectivities to high selectivities (for IP and MY: 3,4-selectivity up to 99%; for OC: trans-1,2-selectivity up to 93% (mm up to 90%); for p-MOPB: 3,4-syndioselectivity (3,4- up to 99%, rrrr up to 96%)). DFT calculations explain the continuous coordination roles of PMs on the regulation of the regio- and stereoselectivity of the polymerization of CDs. In comparison with the traditional strategies, this strategy by adding some common PMs is easier and more convenient, decreasing the synthetic cost and complex operation of new metal catalyst and cocatalyst. Such regio- and stereoselective regulation method by using PMs is not reported for the coordination polymerization of olefins catalyzed by rare-earth metal and early transition metal complexes.


Assuntos
Monoterpenos Acíclicos , Alcenos , Butadienos , Complexos de Coordenação , Hemiterpenos , Metais Terras Raras , Polimerização , Polienos , Catálise
15.
Biosens Bioelectron ; 248: 115998, 2024 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-38176254

RESUMO

The release of isoprene by plants is considered to be an adaptation to the environment. Herein, a highly selective coumarin fluorescent probe (DMIC) was designed for detecting isoprene. When isoprene came into contact with the maleimide of DMIC, an electrophilic addition process took place. The powerful push-pull effect of DMIC was disrupted. Simultaneously, intramolecular charge transfer was initiated. This enabled DMIC to achieve rapid detection of isoprene within 5 min. Furthermore, excellent linearity was observed in the concentration range of 1-560 ppm (R2 = 0.996). A limit of detection is 1.6 ppm. DMIC was applied to in vitro studies of plant release of liberated isoprene. By monitoring the release of isoprene from different tree species throughout the day, the dynamics of isoprene release from plants throughout the day have been successfully revealed. In addition, the release of isoprene varied considerably among different tree species. In particular, the biocompatibility of DMIC allowed for the in vivo detection of isoprene using fluorescence imaging. The results successfully revealed the dynamics of isoprene release in plants under stress. The amount of isoprene that a plant produced increased with the severity of the stress it experienced. This suggested that the level of isoprene content in plants could be used as a preliminary indicator of the physiological health status of plants. This research demonstrates great potential for clarifying signal transduction in biological systems. It provided ideas for further understanding the biology of isoprene.


Assuntos
Técnicas Biossensoriais , Butadienos , Plantas , Hemiterpenos , Cumarínicos
16.
Mol Biotechnol ; 66(1): 56-67, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-37014586

RESUMO

2-C-methyl-D-erythritol-phosphate cytidylyltransferase (MCT) is a key enzyme in the MEP pathway of monoterpene synthesis, catalyzing the generation of 4- (5'-pyrophosphate cytidine)-2-C-methyl-D-erythritol from 2-C-methyl-D-erythritol-4-phosphate. We used homologous cloning strategy to clone gene, LiMCT, in the MEP pathway that may be involved in the regulation of floral fragrance synthesis in the Lilium oriental hybrid 'Sorbonne.' The full-length ORF sequence was 837 bp, encoding 278 amino acids. Bioinformatics analysis showed that the relative molecular weight of LiMCT protein is 68.56 kD and the isoelectric point (pI) is 5.12. The expression pattern of LiMCT gene was found to be consistent with the accumulation sites and emission patterns of floral fragrance monoterpenes in transcriptome data (unpublished). Subcellular localization indicated that the LiMCT protein is located in chloroplasts, which is consistent with the location of MEP pathway genes functioning in plastids to produce isoprene precursors. Overexpression of LiMCT in Arabidopsis thaliana affected the expression levels of MEP and MVA pathway genes, suggesting that overexpression of the LiMCT in A. thaliana affected the metabolic flow of C5 precursors of two different terpene synthesis pathways. The expression of the monoterpene synthase AtTPS14 was elevated nearly fourfold in transgenic A. thaliana compared with the control, and the levels of carotenoids and chlorophylls, the end products of the MEP pathway, were significantly increased in the leaves at full bloom, indicating that LiMCT plays an important role in regulating monoterpene synthesis and in the synthesis of other isoprene-like precursors in transgenic A. thaliana flowers. However, the specific mechanism of LiMCT in promoting the accumulation of isoprene products of the MEP pathway and the biosynthesis of floral monoterpene volatile components needs further investigation.


Assuntos
Arabidopsis , Butadienos , Hemiterpenos , Lilium , Fosfatos Açúcares , Lilium/genética , Lilium/metabolismo , Arabidopsis/genética , Arabidopsis/metabolismo , Monoterpenos/metabolismo , Eritritol/metabolismo , Clonagem Molecular , Regulação da Expressão Gênica de Plantas
17.
Plant Cell Environ ; 47(4): 1099-1117, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38038355

RESUMO

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.


Assuntos
Fotossíntese , Proteômica , Hemiterpenos/metabolismo , Butadienos/metabolismo , Árvores/metabolismo , Pentanos/metabolismo , Folhas de Planta/metabolismo
18.
Nihon Hoshasen Gijutsu Gakkai Zasshi ; 80(2): 155-165, 2024 Feb 20.
Artigo em Japonês | MEDLINE | ID: mdl-38072451

RESUMO

PURPOSE: This study aimed to identify disposable items with low amyloid positron emission tomography (PET) agent radioactivity adsorption for accurate injections using a radiopharmaceutical activity supplier. METHODS: First, we investigated disposable items currently used for amyloid PET agent injection. Next, we measured the residual radioactivity rates of amyloid PET agents on three-way stopcocks, extension tubes, butterfly needles, and indwelling needles to identify disposable items with low radioactivity adsorption. Finally, we evaluated the accuracy of amyloid PET agent injection using the selected disposable items and a radiopharmaceutical activity supplier. RESULTS: The polybutadiene extension tube exhibited a significantly lower residual activity rate than that of the polyvinyl chloride extension tube. Similarly, the indwelling needles showed significantly lower residual activity rate than that of butterfly needles. The dose indicated by a radiopharmaceutical activity supplier was 184.1 MBq, while the dose calibrator measured the radioactivity which flowed into the vial as 170.2 MBq, resulting in an administration accuracy of 8.2%. CONCLUSION: To ensure accurate amyloid PET agent injections, we recommend using polybutadiene extension tubes and indwelling needles due to their lower radioactivity adsorption.


Assuntos
Elastômeros , Tomografia por Emissão de Pósitrons , Compostos Radiofarmacêuticos , Tomografia por Emissão de Pósitrons/métodos , Amiloide , Butadienos
19.
Bioresour Technol ; 393: 130098, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-38040299

RESUMO

Isoprene has numerous industrial applications, including rubber polymer and potential biofuel. Microbial methane-based isoprene production could be a cost-effective and environmentally benign process, owing to a reduced carbon footprint and economical utilization of methane. In this study, Methylococcus capsulatus Bath was engineered to produce isoprene from methane by introducing the exogenous mevalonate (MVA) pathway. Overexpression of MVA pathway enzymes and isoprene synthase from Populus trichocarpa under the control of a phenol-inducible promoter substantially improved isoprene production. M. capsulatus Bath was further engineered using a CRISPR-base editor to disrupt the expression of soluble methane monooxygenase (sMMO), which oxidizes isoprene to cause toxicity. Additionally, optimization of the metabolic flux in the MVA pathway and culture conditions increased isoprene production to 228.1 mg/L, the highest known titer for methanotroph-based isoprene production. The developed methanotroph could facilitate the efficient conversion of methane to isoprene, resulting in the sustainable production of value-added chemicals.


Assuntos
Metano , Methylococcus capsulatus , Metano/metabolismo , Methylococcus capsulatus/genética , Methylococcus capsulatus/metabolismo , Oxigenases/genética , Oxigenases/metabolismo , Hemiterpenos/metabolismo , Butadienos/metabolismo
20.
J Occup Environ Hyg ; 21(1): 13-23, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-37788445

RESUMO

Among the first 20 high-priority chemical substances selected by USEPA to undergo risk evaluation as part of the Toxic Substances Control Act, as amended by the Frank R. Lautenberg Chemical Safety for the 21st Century Act of 2016 is 1,3-butadiene (1,3-BD). Because much of the literature related to occupational exposure to 1,3-BD is associated with the use of the substance in synthetic rubber production and few data have been published for exposures to 1,3-BD manufacturing workers, existing industrial hygiene data collected at facilities where the substance is manufactured or processed as a reactant were compiled and analyzed. The dataset was comprised of personal air samples collected between 2010 and 2019 at facilities located throughout the United States and was compiled into a single database using a uniform data collection template. Data designated by the companies as full-shift were stratified by job group and one of three operational conditions of the workplace: routine, turnaround, and non-routine. Data designated by the companies as short-term and task-level were stratified by task description, sample duration, and operational condition. The final aggregated database contained a total of 5,676 full-shift personal samples. Mean concentrations of 1,3-BD for the job groups ranged from 0.012 ppm to 0.16 ppm. High-end estimates of 1,3-BD air concentrations for the job groups under routine operations ranged from 0.014 ppm to 0.23 ppm. The aggregated database also included 1,063 short-term and task-level personal samples. For short-term samples (< =15 min), mean concentrations ranged from 0.49 ppm to 3.9 ppm, with the highest concentrations observed for the cleaning and maintaining equipment tasks. For task samples with durations greater than 15 min, mean concentrations ranged from 0.49 to 3.6 ppm, with the highest concentrations observed for the unloading and loading task. In addition to the personal air sampling records, information on the use of PPE during various tasks was compiled and analyzed. This data set provides robust quantitative air concentration data and exposure control information for which occupational exposures to 1,3-BD in the Manufacturing and Processing as a Reactant condition of use can be assessed.


Assuntos
Indústria Química , Exposição Ocupacional , Humanos , Butadienos , Indústrias , Estados Unidos
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