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1.
Cell ; 152(1-2): 290-303, 2013 Jan 17.
Artigo em Inglês | MEDLINE | ID: mdl-23332761

RESUMO

Autophagy is a stress response protecting cells from unfavorable conditions, such as nutrient starvation. The class III phosphatidylinositol-3 kinase, Vps34, forms multiple complexes and regulates both intracellular vesicle trafficking and autophagy induction. Here, we show that AMPK plays a key role in regulating different Vps34 complexes. AMPK inhibits the nonautophagy Vps34 complex by phosphorylating T163/S165 in Vps34 and therefore suppresses overall PI(3)P production and protects cells from starvation. In parallel, AMPK activates the proautophagy Vps34 complex by phosphorylating S91/S94 in Beclin1 to induce autophagy. Atg14L, an autophagy-essential gene present only in the proautophagy Vps34 complex, inhibits Vps34 phosphorylation but increases Beclin1 phosphorylation by AMPK. As such, Atg14L dictates the differential regulation (either inhibition or activation) of different Vps34 complexes in response to glucose starvation. Our study reveals an intricate molecular regulation of Vps34 complexes by AMPK in nutrient stress response and autophagy.


Assuntos
Autofagia , Classe III de Fosfatidilinositol 3-Quinases/metabolismo , Proteínas Quinases/metabolismo , Quinases Proteína-Quinases Ativadas por AMP , Sequência de Aminoácidos , Animais , Proteínas Reguladoras de Apoptose/química , Proteínas Reguladoras de Apoptose/metabolismo , Proteínas Relacionadas à Autofagia , Proteína Beclina-1 , Classe III de Fosfatidilinositol 3-Quinases/genética , Glucose/metabolismo , Camundongos , Dados de Sequência Molecular , Complexos Multiproteicos/metabolismo , Fosforilação , Proteínas Quinases/química , Proteínas Quinases/genética , Alinhamento de Sequência , Proteínas de Transporte Vesicular/metabolismo
2.
Angew Chem Int Ed Engl ; 63(19): e202401555, 2024 May 06.
Artigo em Inglês | MEDLINE | ID: mdl-38494454

RESUMO

The electrochemical stability window of water is known to vary with the type and concentration of dissolved salts. However, the underlying influence of ions on the thermodynamic stability of aqueous solutions has not been fully understood. Here, we investigated the electrolytic behaviors of aqueous electrolytes as a function of different ions. Our findings indicate that ions with high ionic potentials, i.e., charge density, promote the formation of their respective hydration structures, enhancing electrolytic reactions via an inductive effect, particularly for small cations. Conversely, ions with lower ionic potentials increase the proportion of free water molecules-those not engaged in hydration shells or hydrogen-bonding networks-leading to greater electrolytic stability. Furthermore, we observe that the chemical environment created by bulky ions with lower ionic potentials impedes electrolytic reactions by frustrating the solvation of protons and hydroxide ions, the products of oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), respectively. We found that the solvation of protons plays a more substantial role than that of hydroxide, which explains a greater shift for OER than for HER, a puzzle that cannot be rationalized by the notion of varying O-H bond strengths of water. These insights will help the design of aqueous systems.

3.
Phys Chem Chem Phys ; 25(23): 15624-15634, 2023 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-37211909

RESUMO

The incorporation of noncanonical amino acids (ncAAs) into fluorescent proteins is promising for red-shifting their fluorescence and benefiting tissue imaging with deep penetration and low phototoxicity. However, ncAA-based red fluorescent proteins (RFPs) have been rare. The 3-aminotyrosine modified superfolder green fluorescent protein (aY-sfGFP) represents a recent advance, yet the molecular mechanism for its red-shifted fluorescence remains elusive while its dim fluorescence hinders applications. Herein, we implement femtosecond stimulated Raman spectroscopy to obtain structural fingerprints in the electronic ground state and reveal that aY-sfGFP possesses a GFP-like instead of RFP-like chromophore. Red color of aY-sfGFP intrinsically arises from a unique "double-donor" chromophore structure that raises ground-state energy and enhances charge transfer, notably differing from the conventional conjugation mechanism. We further developed two aY-sfGFP mutants (E222H and T203H) with significantly improved (∼12-fold higher) brightness by rationally restraining the chromophore's nonradiative decay through electronic and steric effects, aided by solvatochromic and fluorogenic studies of the model chromophore in solution. This study thus provides functional mechanisms and generalizable insights into ncAA-RFPs with an efficient route for engineering redder and brighter fluorescent proteins.


Assuntos
Proteínas de Fluorescência Verde , Proteínas de Fluorescência Verde/química , Proteínas de Fluorescência Verde/genética , Cor , Modelos Moleculares , Estrutura Terciária de Proteína , Mutação , Aminoácidos/química , Aminoácidos/genética , Variação Genética
4.
Int J Mol Sci ; 24(15)2023 Jul 26.
Artigo em Inglês | MEDLINE | ID: mdl-37569365

RESUMO

The versatile functions of fluorescent proteins (FPs) as fluorescence biomarkers depend on their intrinsic chromophores interacting with the protein environment. Besides X-ray crystallography, vibrational spectroscopy represents a highly valuable tool for characterizing the chromophore structure and revealing the roles of chromophore-environment interactions. In this work, we aim to benchmark the ground-state vibrational signatures of a series of FPs with emission colors spanning from green, yellow, orange, to red, as well as the solvated model chromophores for some of these FPs, using wavelength-tunable femtosecond stimulated Raman spectroscopy (FSRS) in conjunction with quantum calculations. We systematically analyzed and discussed four factors underlying the vibrational properties of FP chromophores: sidechain structure, conjugation structure, chromophore conformation, and the protein environment. A prominent bond-stretching mode characteristic of the quinoidal resonance structure is found to be conserved in most FPs and model chromophores investigated, which can be used as a vibrational marker to interpret chromophore-environment interactions and structural effects on the electronic properties of the chromophore. The fundamental insights gained for these light-sensing units (e.g., protein active sites) substantiate the unique and powerful capability of wavelength-tunable FSRS in delineating FP chromophore properties with high sensitivity and resolution in solution and protein matrices. The comprehensive characterization for various FPs across a colorful palette could also serve as a solid foundation for future spectroscopic studies and the rational engineering of FPs with diverse and improved functions.


Assuntos
Análise Espectral Raman , Análise Espectral Raman/métodos , Proteínas de Fluorescência Verde/metabolismo , Domínio Catalítico
5.
J Environ Manage ; 340: 117965, 2023 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-37121003

RESUMO

Straw return can improve crop yield as well as soil organic carbon (SOC) but may raise the possibility of N2O and CH4 emissions. However, few studies have compared the effects of straw return on the yield, SOC, and N2O emissions of various crops. Which management strategies are the best for balancing yield, SOC, and emission reduction for various crops needs to be clarified. A meta-analysis containing 2269 datasets collected from 369 studies was conducted to investigate the influence of agricultural management strategies on yield increase, soil carbon sequestration, and emission reduction in various crops after the straw return. Analytical results indicated that, on average, straw return increased the yield of rice, wheat, and maize by 5.04%, 8.09%, and 8.71%, respectively. Straw return increased maize N2O emissions by 14.69% but did not significantly affect wheat N2O emissions. Interestingly, straw return reduced the rice N2O emissions by 11.43% but increased the CH4 emissions by 72.01%. The recommended nitrogen application amounts for balancing yield, SOC, and emission reduction varied among the three crops, while the recommended straw return amounts were more than 9000 kg/ha. The optimal tillage and straw return strategies for rice, wheat, and maize were plow tillage combined with incorporation, rotary tillage combined with incorporation, and no-tillage combined with mulching, respectively. A straw return duration of 5-10 years for rice and maize and ≤5 years for wheat was recommended. These findings provide optimal agricultural management strategies after straw return to balance the crop yield, SOC, and emission reduction for China's three major grain crops.


Assuntos
Oryza , Solo , Sequestro de Carbono , Carbono/análise , Agricultura/métodos , Produtos Agrícolas , Zea mays , Triticum/metabolismo , Grão Comestível/química , China , Óxido Nitroso/metabolismo
6.
Molecules ; 28(2)2023 Jan 06.
Artigo em Inglês | MEDLINE | ID: mdl-36677656

RESUMO

Nitrophenols are a group of small organic molecules with significant environmental implications from the atmosphere to waterways. In this work, we investigate a series of nitrophenols and nitrophenolates, with the contrasting ortho-, meta-, and para-substituted nitro group to the phenolic hydroxy or phenolate oxygen site (2/3/4NP or NP-), implementing a suite of steady-state and time-resolved spectroscopic techniques that include UV/Visible spectroscopy, femtosecond transient absorption (fs-TA) spectroscopy with probe-dependent and global analysis, and femtosecond stimulated Raman spectroscopy (FSRS), aided by quantum calculations. The excitation-dependent (400 and 267 nm) electronic dynamics in water and methanol, for six protonated or deprotonated nitrophenol molecules (three regioisomers in each set), enable a systematic investigation of the excited-state dynamics of these functional "nanomachines" that can undergo nitro-group twisting (as a rotor), excited-state intramolecular or intermolecular proton transfer (donor-acceptor, ESIPT, or ESPT), solvation, and cooling (chromophore) events on molecular timescales. In particular, the meta-substituted compound 3NP or 3NP- exhibits the strongest charge-transfer character with FSRS signatures (e.g., C-N peak frequency), and thus, does not favor nitroaromatic twist in the excited state, while the ortho-substituted compound 2NP can undergo ESIPT in water and likely generate nitrous acid (HONO) after 267 nm excitation. The delineated mechanistic insights into the nitro-substituent-location-, protonation-, solvent-, and excitation-wavelength-dependent effects on nitrophenols, in conjunction with the ultraviolet-light-induced degradation of 2NP in water, substantiates an appealing discovery loop to characterize and engineer functional molecules for environmental applications.

7.
Molecules ; 28(8)2023 Apr 16.
Artigo em Inglês | MEDLINE | ID: mdl-37110741

RESUMO

Proton transfer processes of organic molecules are key to charge transport and photoprotection in biological systems. Among them, excited-state intramolecular proton transfer (ESIPT) reactions are characterized by quick and efficient charge transfer within a molecule, resulting in ultrafast proton motions. The ESIPT-facilitated interconversion between two tautomers (PS and PA) comprising the tree fungal pigment Draconin Red in solution was investigated using a combination of targeted femtosecond transient absorption (fs-TA) and excited-state femtosecond stimulated Raman spectroscopy (ES-FSRS) measurements. Transient intensity (population and polarizability) and frequency (structural and cooling) dynamics of -COH rocking and -C=C, -C=O stretching modes following directed stimulation of each tautomer elucidate the excitation-dependent relaxation pathways, particularly the bidirectional ESIPT progression out of the Franck-Condon region to the lower-lying excited state, of the intrinsically heterogeneous chromophore in dichloromethane solvent. A characteristic overall excited-state PS-to-PA transition on the picosecond timescale leads to a unique "W"-shaped excited-state Raman intensity pattern due to dynamic resonance enhancement with the Raman pump-probe pulse pair. The ability to utilize quantum mechanics calculations in conjunction with steady-state electronic absorption and emission spectra to induce disparate excited-state populations in an inhomogeneous mixture of similar tautomers has broad implications for the modeling of potential energy surfaces and delineation of reaction mechanisms in naturally occurring chromophores. Such fundamental insights afforded by in-depth analysis of ultrafast spectroscopic datasets are also beneficial for future development of sustainable materials and optoelectronics.

8.
Angew Chem Int Ed Engl ; 62(5): e202212209, 2023 01 26.
Artigo em Inglês | MEDLINE | ID: mdl-36440527

RESUMO

Large Stokes shift (LSS) red fluorescent proteins (RFPs) are highly desirable for bioimaging advances. The RFP mKeima, with coexisting cis- and trans-isomers, holds significance as an archetypal system for LSS emission due to excited-state proton transfer (ESPT), yet the mechanisms remain elusive. We implemented femtosecond stimulated Raman spectroscopy (FSRS) and various time-resolved electronic spectroscopies, aided by quantum calculations, to dissect the cis- and trans-mKeima photocycle from ESPT, isomerization, to ground-state proton transfer in solution. This work manifests the power of FSRS with global analysis to resolve Raman fingerprints of intermediate states. Importantly, the deprotonated trans-isomer governs LSS emission at 620 nm, while the deprotonated cis-isomer's 520 nm emission is weak due to an ultrafast cis-to-trans isomerization. Complementary spectroscopic techniques as a table-top toolset are thus essential to study photochemistry in physiological environments.


Assuntos
Prótons , Análise Espectral Raman , Proteínas Luminescentes/química , Análise Espectral Raman/métodos , Isomerismo , Proteínas de Fluorescência Verde/química , Proteína Vermelha Fluorescente
9.
Angew Chem Int Ed Engl ; 62(35): e202307212, 2023 Aug 28.
Artigo em Inglês | MEDLINE | ID: mdl-37407432

RESUMO

Aqueous electrolytes typically suffer from poor electrochemical stability; however, eutectic aqueous solutions-25 wt.% LiCl and 62 wt.% H3 PO4 -cooled to -78 °C exhibit a significantly widened stability window. Integrated experimental and simulation results reveal that, upon cooling, Li+ ions become less hydrated and pair up with Cl- , ice-like water clusters form, and H⋅⋅⋅Cl- bonding strengthens. Surprisingly, this low-temperature solvation structure does not strengthen water molecules' O-H bond, bucking the conventional wisdom that increasing water's stability requires stiffening the O-H covalent bond. We propose a more general mechanism for water's low temperature inertness in the electrolyte: less favorable solvation of OH- and H+ , the byproducts of hydrogen and oxygen evolution reactions. To showcase this stability, we demonstrate an aqueous Li-ion battery using LiMn2 O4 cathode and CuSe anode with a high energy density of 109 Wh/kg. These results highlight the potential of aqueous batteries for polar and extraterrestrial missions.

10.
Opt Express ; 30(3): 4028-4045, 2022 Jan 31.
Artigo em Inglês | MEDLINE | ID: mdl-35209649

RESUMO

Secchi disk depth (SDD) has long been considered as a reliable proxy for lake clarity, and an important indicator of the aquatic ecosystems. Meteorological and anthropogenic factors can affect SDD, but the mechanism of these effects and the potential control of climate change are poorly understood. Preliminary research at Lake Khanka (international shallow lake on the China-Russia border) had led to the hypothesis that climatic factors, through their impact on suspended particulate matter (SPM) concentration, are key drivers of SDD variability. To verify the hypothesis, Landsat and MODIS images were used to examine temporal trend in these parameters. For that analysis, the novel SPM index (SPMI) was developed, through incorporation of SPM concentration effect on spectral radiance, and was satisfactorily applied to both Landsat (R2 = 0.70, p < 0.001) and MODIS (R2 = 0.78, p < 0.001) images to obtain remote estimates of SPM concentration. Further, the SPMI algorithm was successfully applied to the shallow lakes Hulun, Chao and Hongze, demonstrating its portability. Through analysis of the temporal trend (1984-2019) in SDD and SPM, this study demonstrated that variation in SPM concentration was the dominant driver (explaining 63% of the variation as opposed to 2% due to solar radiation) of SDD in Lake Khanka, thus supporting the study hypothesis. Furthermore, we speculated that variation in wind speed, probably impacted by difference in temperature between lake surface and surrounding landscapes (greater difference between 1984-2009 than after 2010), may have caused varying degree of sediment resuspension, ultimately controlling SPM and SDD variation in Lake Khanka.

11.
Glob Chang Biol ; 28(7): 2327-2340, 2022 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-34995391

RESUMO

Algal blooms (ABs) in inland lakes have caused adverse ecological effects, and health impairment of animals and humans. We used archived Landsat images to examine ABs in lakes (>1 km2 ) around the globe over a 37-year time span (1982-2018). Out of the 176032 lakes with area >1 km2 detected globally, 863 were impacted by ABs, 708 had sufficiently long records to define a trend, and 66% exhibited increasing trends in frequency ratio (FRQR, ratio of the number of ABs events observed in a year in a given lake to the number of available Landsat images for that lake) or area ratio (AR, ratio of annual maximum area covered by ABs observed in a lake to the surface area of that lake), while 34% showed a decreasing trend. Across North America, an intensification of ABs severity was observed for FRQR (p < .01) and AR (p < .01) before 1999, followed by a decrease in ABs FRQR (p < .01) and AR (p < .05) after the 2000s. The strongest intensification of ABs was observed in Asia, followed by South America, Africa, and Europe. No clear trend was detected for the Oceania. Across climatic zones, the contributions of anthropogenic factors to ABs intensification (16.5% for fertilizer, 19.4% for gross domestic product, and 18.7% for population) were slightly stronger than climatic drivers (10.1% for temperature, 11.7% for wind speed, 16.8% for pressure, and for 11.6% for rainfall). Collectively, these divergent trends indicate that consideration of anthropogenic factors as well as climate change should be at the forefront of management policies aimed at reducing the severity and frequency of ABs in inland waters.


Assuntos
Monitoramento Ambiental , Eutrofização , Animais , Mudança Climática , Monitoramento Ambiental/métodos , Lagos , Vento
12.
Int J Mol Sci ; 23(12)2022 Jun 09.
Artigo em Inglês | MEDLINE | ID: mdl-35742900

RESUMO

The advancement of super-resolution imaging (SRI) relies on fluorescent proteins with novel photochromic properties. Using light, the reversibly switchable fluorescent proteins (RSFPs) can be converted between bright and dark states for many photocycles and their emergence has inspired the invention of advanced SRI techniques. The general photoswitching mechanism involves the chromophore cis-trans isomerization and proton transfer for negative and positive RSFPs and hydration-dehydration for decoupled RSFPs. However, a detailed understanding of these processes on ultrafast timescales (femtosecond to millisecond) is lacking, which fundamentally hinders the further development of RSFPs. In this review, we summarize the current progress of utilizing various ultrafast electronic and vibrational spectroscopies, and time-resolved crystallography in investigating the on/off photoswitching pathways of RSFPs. We show that significant insights have been gained for some well-studied proteins, but the real-time "action" details regarding the bidirectional cis-trans isomerization, proton transfer, and intermediate states remain unclear for most systems, and many other relevant proteins have not been studied yet. We expect this review to lay the foundation and inspire more ultrafast studies on existing and future engineered RSFPs. The gained mechanistic insights will accelerate the rational development of RSFPs with enhanced two-way switching rate and efficiency, better photostability, higher brightness, and redder emission colors.


Assuntos
Prótons , Cristalografia , Proteínas de Fluorescência Verde/química , Proteínas Luminescentes/química , Proteínas Luminescentes/genética , Análise Espectral
13.
J Environ Manage ; 322: 116099, 2022 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-36058069

RESUMO

Appropriate nitrogen (N) application increases crop yield, while its unreasonable application results in environmental problem. Determining the appropriate N application rate is the key to sustainable development. Here, the denitrification-decomposition (DNDC) model was used to analyze the effects of N fertilizer on maize yields, economic benefits, nitrate leaching, and nitrous oxide emissions in China. The N application rate for the trade-off between economy and environment at the county scale was further determined. The geodetector model was used to identify the main driving factors and their interactions of the recommended N rate in each agricultural zone. The results showed that the recommended N rate was generally high in the northwest but low in the south, consistent with the spatial patterns of yield potential. However, clay soils with clay ratios greater than 34% in southern China and sandy soils with bulk densities greater than 1.5 g cm-3 on the Huanghuaihai Plain experienced high N levels and low yields, and thus soils need to be improved. Potential grain yield was the main driving factor in most zones, yet its effects gradually weakened from north to south. The influence of soil characteristics increased from north to south. It was found that the current average N application rate of farmers in China was 249 kg N/ha, and 86.55% of counties had excessive N applications. Compared to the regional optimal N rate at a regional scale, a differentiated N application strategy at the county scale determined in this study increased maize yield and economic benefit by 10.51% and 10.85%, respectively, and reduced N2O emissions and NO3- leaching by 28.72% and 33.60%, respectively. The current research provides a scientific basis for China to formulate a win-win N management strategy for economy and environment and provides a method reference for other countries.


Assuntos
Fertilizantes , Nitrogênio , Agricultura/métodos , China , Argila , Análise Fatorial , Fertilizantes/análise , Nitratos/análise , Nitrogênio/análise , Óxido Nitroso/análise , Solo , Zea mays
14.
Chemistry ; 27(71): 17736-17750, 2021 Dec 20.
Artigo em Inglês | MEDLINE | ID: mdl-34545971

RESUMO

Recent advances in sustainable optoelectronics including photovoltaics, light-emitting diodes, transistors, and semiconductors have been enabled by π-conjugated organic molecules. A fundamental understanding of light-matter interactions involving these materials can be realized by time-resolved electronic and vibrational spectroscopies. In this Minireview, the photoinduced mechanisms including charge/energy transfer, electronic (de)localization, and excited-state proton transfer are correlated with functional properties encompassing optical absorption, fluorescence quantum yield, conductivity, and photostability. Four naturally derived molecules (xylindein, dimethylxylindein, alizarin, indigo) with ultrafast spectral insights showcase efficient energy dissipation involving H-bonding networks and proton motions, which yield high photostability. Rational design principles derived from such investigations could increase the efficiency for light harvesting, triplet formation, and photosensitivity for improved and versatile optoelectronic performance.

15.
Chemistry ; 27(18): 5627-5631, 2021 Mar 26.
Artigo em Inglês | MEDLINE | ID: mdl-33543812

RESUMO

Organic semiconductor materials have recently gained momentum due to their non-toxicity, low cost, and sustainability. Xylindein is a remarkably photostable pigment secreted by fungi that grow on decaying wood, and its relatively strong electronic performance is enabled by π-π stacking and hydrogen-bonding network that promote charge transport. Herein, femtosecond transient absorption spectroscopy with a near-IR probe was used to unveil a rapid excited-state intramolecular proton transfer reaction. Conformational motions potentially lead to a conical intersection that quenches fluorescence in the monomeric state. In concentrated solutions, nascent aggregates exhibit a faster excited state lifetime due to excimer formation, confirmed by the excimer→charge-transfer excited-state absorption band of the xylindein thin film, thus limiting its optoelectronic performance. Therefore, extending the xylindein sidechains with branched alkyl groups may hinder the excimer formation and improve optoelectronic properties of naturally derived materials.


Assuntos
Compostos Policíclicos , Prótons , Fungos , Ligação de Hidrogênio , Fenóis
16.
Chemistry ; 27(35): 8946-8950, 2021 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-33938061

RESUMO

Fluorescence-activating proteins (FAPs) that bind a chromophore and activate its fluorescence have gained popularity in bioimaging. The fluorescence-activating and absorption-shifting tag (FAST) is a light-weight FAP that enables fast reversible fluorogen binding, thus advancing multiplex and super-resolution imaging. However, the rational design of FAST-specific fluorogens with large fluorescence enhancement (FE) remains challenging. Herein, a new fluorogen directly engineered from green fluorescent protein (GFP) chromophore by a unique double-donor-one-acceptor strategy, which exhibits an over 550-fold FE upon FAST binding and a high extinction coefficient of approximately 100,000 M-1 cm-1 , is reported. Correlation analysis of the excited state nonradiative decay rates and environmental factors reveal that the large FE is caused by nonpolar protein-fluorogen interactions. Our deep insights into structure-function relationships could guide the rational design of bright fluorogens for live-cell imaging with extended spectral properties such as redder emissions.


Assuntos
Corantes Fluorescentes , Proteínas de Fluorescência Verde/genética , Microscopia de Fluorescência
17.
Annu Rev Phys Chem ; 71: 239-265, 2020 04 20.
Artigo em Inglês | MEDLINE | ID: mdl-32075503

RESUMO

The structure-function relationships of biomolecules have captured the interest and imagination of the scientific community and general public since the field of structural biology emerged to enable the molecular understanding of life processes. Proteins that play numerous functional roles in cellular processes have remained in the forefront of research, inspiring new characterization techniques. In this review, we present key theoretical concepts and recent experimental strategies using femtosecond stimulated Raman spectroscopy (FSRS) to map the structural dynamics of proteins, highlighting the flexible chromophores on ultrafast timescales. In particular, wavelength-tunable FSRS exploits dynamic resonance conditions to track transient-species-dependent vibrational motions, enabling rational design to alter functions. Various ways of capturing excited-state chromophore structural snapshots in the time and/or frequency domains are discussed. Continuous development of experimental methodologies, synergistic correlation with theoretical modeling, and the expansion to other nonequilibrium, photoswitchable, and controllable protein systems will greatly advance the chemical, physical, and biological sciences.


Assuntos
Proteínas/química , Análise Espectral Raman/métodos , Transferência de Energia , Modelos Químicos , Simulação de Dinâmica Molecular , Relação Estrutura-Atividade
18.
Environ Sci Technol ; 55(5): 2929-2938, 2021 03 02.
Artigo em Inglês | MEDLINE | ID: mdl-33595308

RESUMO

The proliferation of algal blooms (ABs) in lakes and reservoirs (L&Rs) poses a threat to water quality and the ecological health of aquatic communities. With global climate change, there is a concern that the frequency and geographical expansion of ABs in L&Rs could increase. China has experienced rapid economic growth and major land-use changes over the last several decades and therefore provides an excellent context for such an analysis. About 289,600 Landsat images were used to examine the spatiotemporal distribution of ABs in L&Rs (>1 km2) across China (1983-2017). Results showed significant changes in the temporal slope of the sum of normalized area (0.26), frequency (2.28), duration (6.14), and early outbreak (-3.48) of AB events in L&Rs across China. Specifically, AB-impacted water bodies expanded longitudinally, and the time range of AB observation has expanded starting in the 2000s. Spearman correlation and random forest regression analyses further indicated that, among climatic factors, wind speed and temperature contributed the most to AB expansion. Overall, anthropogenic forces have overridden the imprints of climatic factors on the temporal evolution of ABs in China's L&Rs and therefore could inform policy decisions for the management of these resources.


Assuntos
Monitoramento Ambiental , Lagos , China , Eutrofização , Qualidade da Água
19.
Phys Chem Chem Phys ; 23(27): 14636-14648, 2021 Jul 14.
Artigo em Inglês | MEDLINE | ID: mdl-34212170

RESUMO

Since green fluorescent protein (GFP) has revolutionized molecular and cellular biology for about three decades, there has been a keen interest in understanding, designing, and controlling the fluorescence properties of GFP chromophore (i.e., HBDI) derivatives from the protein matrix to solution. Amongst these cross-disciplinary efforts, the elucidation of excited-state dynamics of HBDI derivatives holds the key to correlating the light-induced processes and fluorescence quantum yield (FQY). Herein, we implement steady-state electronic spectroscopy, femtosecond transient absorption (fs-TA), femtosecond stimulated Raman spectroscopy (FSRS), and quantum calculations to study a series of mono- and dihalogenated HBDI derivatives (X = F, Cl, Br, 2F, 2Cl, and 2Br) in basic aqueous solution, gaining new insights into the photophysical reaction coordinates. In the excited state, the halogenated "floppy" chromophores exhibit an anti-heavy atom effect, reflected by strong correlations between FQY vs. Franck-Condon energy (EFC) or Stokes shift, and knrvs. EFC, as well as a swift bifurcation into the I-ring (major) and P-ring (minor) twisting motions. In the ground state, both ring-twisting motions become more susceptible to sterics and exhibit spectral signatures from the halogen-dependent hot ground-state absorption band decay in TA data. We envision this type of systematic analysis of the halogenated HBDI derivatives to provide guiding principles for the site-specific modification of GFP chromophores, and expand design space for brighter and potentially photoswitchable organic chemical probes in aqueous solution with discernible spectral signatures throughout the photocycle.


Assuntos
Corantes Fluorescentes/química , Proteínas de Fluorescência Verde/química , Halogenação , Cinética , Luz , Modelos Moleculares , Processos Fotoquímicos , Conformação Proteica , Espectrometria de Fluorescência , Relação Estrutura-Atividade
20.
Environ Res ; 201: 111579, 2021 10.
Artigo em Inglês | MEDLINE | ID: mdl-34197817

RESUMO

Reservoirs were critical sources of drinking water for many large cities around the world, but progress in the development of large-scale monitoring protocols to obtain timely information about water quality had been hampered by the complex nature of inland waters and the various optical conditions exhibited by these aquatic ecosystems. In this study, we systematically investigated the absorption coefficient of different optically-active constituents (OACs) in 120 reservoirs of different trophic states across five eco-regions in China. The relationships were found between phytoplankton absorption coefficient at 675 nm (aph (675)) and Chlorophyll a (Chla) concentration in different regions (R2:0.60-0.82). The non-algal particle (NAP) absorption coefficient (aNAP) showed an increasing trend for reservoirs with trophic states. Significant correlation (p < 0.05) was observed between chromophoric dissolved organic matter (CDOM) absorption and water chemical parameters. The influencing factors for contributing the relative proportion of OACs absorption including the hydrological factors and water quality factors were analyzed. The non-water absorption budget from our data showed the variations of the dominant absorption types which underscored the need to develop and parameterize region-specific bio-optical models for large-scale assessment in water reservoirs.


Assuntos
Ecossistema , Fitoplâncton , China , Clorofila A , Hidrologia
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