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1.
Physiol Rev ; 100(4): 1779-1837, 2020 10 01.
Article in English | MEDLINE | ID: mdl-31999509

ABSTRACT

The evolution of the circulatory system from invertebrates to mammals has involved the passage from an open system to a closed in-parallel system via a closed in-series system, accompanying the increasing complexity and efficiency of life's biological functions. The archaic heart enables pulsatile motion waves of hemolymph in invertebrates, and the in-series circulation in fish occurs with only an endothelium, whereas mural smooth muscle cells appear later. The present review focuses on evolution of the circulatory system. In particular, we address how and why this evolution took place from a closed, flowing, longitudinal conductance at low pressure to a flowing, highly pressurized and bifurcating arterial compartment. However, although arterial pressure was the latest acquired hemodynamic variable, the general teleonomy of the evolution of species is the differentiation of individual organ function, supported by specific fueling allowing and favoring partial metabolic autonomy. This was achieved via the establishment of an active contractile tone in resistance arteries, which permitted the regulation of blood supply to specific organ activities via its localized function-dependent inhibition (active vasodilation). The global resistance to viscous blood flow is the peripheral increase in frictional forces caused by the tonic change in arterial and arteriolar radius, which backscatter as systemic arterial blood pressure. Consequently, the arterial pressure gradient from circulating blood to the adventitial interstitium generates the unidirectional outward radial advective conductance of plasma solutes across the wall of conductance arteries. This hemodynamic evolution was accompanied by important changes in arterial wall structure, supported by smooth muscle cell functional plasticity, including contractility, matrix synthesis and proliferation, endocytosis and phagocytosis, etc. These adaptive phenotypic shifts are due to epigenetic regulation, mainly related to mechanotransduction. These paradigms actively participate in cardio-arterial pathologies such as atheroma, valve disease, heart failure, aneurysms, hypertension, and physiological aging.


Subject(s)
Cardiovascular Diseases/genetics , Cardiovascular Physiological Phenomena/genetics , Genetic Predisposition to Disease , Hemodynamics , Muscle, Smooth, Vascular/cytology , Humans
2.
Proc Natl Acad Sci U S A ; 121(6): e2313962121, 2024 Feb 06.
Article in English | MEDLINE | ID: mdl-38306480

ABSTRACT

Ultralight architected materials enabled by advanced manufacturing processes have achieved density-normalized strength and stiffness properties that are inaccessible to bulk materials. However, the majority of this work has focused on static loading and elastic-wave propagation. Fundamental understanding of the mechanical behavior of architected materials under large-deformation dynamic conditions remains limited, due to the complexity of mechanical responses and shortcomings of characterization methods. Here, we present a microscale suspended-plate impact testing framework for three-dimensional micro-architected materials, where supersonic microparticles to velocities of up to 850 m/s are accelerated against a substrate-decoupled architected material to quantify its energy dissipation characteristics. Using ultra-high-speed imaging, we perform in situ quantification of the impact energetics on two types of architected materials as well as their constituent nonarchitected monolithic polymer, indicating a 47% or greater increase in mass-normalized energy dissipation under a given impact condition through use of architecture. Post-mortem characterization, supported by a series of quasi-static experiments and high-fidelity simulations, shed light on two coupled mechanisms of energy dissipation: material compaction and particle-induced fracture. Together, experiments and simulations indicate that architecture-specific resistance to compaction and fracture can explain a difference in dynamic impact response across architectures. We complement our experimental and numerical efforts with dimensional analysis which provides a predictive framework for kinetic-energy absorption as a function of material parameters and impact conditions. We envision that enhanced understanding of energy dissipation mechanisms in architected materials will serve to define design considerations toward the creation of lightweight impact-mitigating materials for protective applications.

3.
Proc Natl Acad Sci U S A ; 120(22): e2220033120, 2023 May 30.
Article in English | MEDLINE | ID: mdl-37235635

ABSTRACT

The complex motility of bacteria, ranging from single-swimmer behaviors such as chemotaxis to collective dynamics, including biofilm formation and active matter phenomena, is driven by their microscale propellers. Despite extensive study of swimming flagellated bacteria, the hydrodynamic properties of their helical-shaped propellers have never been directly measured. The primary challenges to directly studying microscale propellers are 1) their small size and fast, correlated motion, 2) the necessity of controlling fluid flow at the microscale, and 3) isolating the influence of a single propeller from a propeller bundle. To solve the outstanding problem of characterizing the hydrodynamic properties of these propellers, we adopt a dual statistical viewpoint that connects to the hydrodynamics through the fluctuation-dissipation theorem (FDT). We regard the propellers as colloidal particles and characterize their Brownian fluctuations, described by 21 diffusion coefficients for translation, rotation, and correlated translation-rotation in a static fluid. To perform this measurement, we applied recent advances in high-resolution oblique plane microscopy to generate high-speed volumetric movies of fluorophore-labeled, freely diffusing Escherichia coli flagella. Analyzing these movies with a bespoke helical single-particle tracking algorithm, we extracted trajectories, calculated the full set of diffusion coefficients, and inferred the average propulsion matrix using a generalized Einstein relation. Our results provide a direct measurement of a microhelix's propulsion matrix and validate proposals that the flagella are highly inefficient propellers, with a maximum propulsion efficiency of less than 3%. Our approach opens broad avenues for studying the motility of particles in complex environments where direct hydrodynamic approaches are not feasible.

4.
Proc Natl Acad Sci U S A ; 120(15): e2300257120, 2023 Apr 11.
Article in English | MEDLINE | ID: mdl-37018200

ABSTRACT

Nanoparticles with highly asymmetric sizes and charges that self-assemble into crystals via electrostatics may exhibit behaviors reminiscent of those of metals or superionic materials. Here, we use coarse-grained molecular simulations with underdamped Langevin dynamics to explore how a binary charged colloidal crystal reacts to an external electric field. As the field strength increases, we find transitions from insulator (ionic state), to superionic (conductive state), to laning, to complete melting (liquid state). In the superionic state, the resistivity decreases with increasing temperature, which is contrary to metals, yet the increment decreases as the electric field becomes stronger. Additionally, we verify that the dissipation of the system and the fluctuation of charge currents obey recently developed thermodynamic uncertainty relation. Our results describe charge transport mechanisms in colloidal superionic conductors.

5.
Semin Cell Dev Biol ; 138: 83-93, 2023 03 30.
Article in English | MEDLINE | ID: mdl-35317962

ABSTRACT

Developing embryos are metabolically active, open systems that constantly exchange matter and energy with their environment. They function out of thermodynamic equilibrium and continuously use metabolic pathways to obtain energy from maternal nutrients, in order to fulfill the energetic requirements of growth and development. While an increasing number of studies highlight the role of metabolism in different developmental contexts, the physicochemical basis of embryogenesis, or how cellular processes use energy and matter to act together and transform a zygote into an adult organism, remains unknown. As we obtain a better understanding of metabolism, and benefit from current technology development, it is a promising time to revisit the energetic cost of development and how energetic principles may govern embryogenesis. Here, we review recent advances in methodology to measure and infer energetic parameters in developing embryos. We highlight a potential common pattern in embryonic energy expenditure and metabolic strategy across animal embryogenesis, and discuss challenges and open questions in developmental energetics.


Subject(s)
Embryonic Development , Energy Metabolism , Animals
6.
Plant J ; 118(5): 1423-1438, 2024 Jun.
Article in English | MEDLINE | ID: mdl-38402588

ABSTRACT

This study investigates photoreceptor's role in the adaption of photosynthetic apparatus to high light (HL) intensity by examining the response of tomato wild type (WT) (Solanum lycopersicum L. cv. Moneymaker) and tomato mutants (phyA, phyB1, phyB2, cry1) plants to HL. Our results showed a photoreceptor-dependent effect of HL on the maximum quantum yield of photosystem II (Fv/Fm) with phyB1 exhibiting a decrease, while phyB2 exhibiting an increase in Fv/Fm. HL resulted in an increase in the efficient quantum yield of photosystem II (ΦPSII) and a decrease in the non-photochemical quantum yields (ΦNPQ and ΦN0) solely in phyA. Under HL, phyA showed a significant decrease in the energy-dependent quenching component of NPQ (qE), while phyB2 mutants showed an increase in the state transition (qT) component. Furthermore, ΔΔFv/Fm revealed that PHYB1 compensates for the deficit of PHYA in phyA mutants. PHYA signaling likely emerges as the dominant effector of PHYB1 and PHYB2 signaling within the HL-induced signaling network. In addition, PHYB1 compensates for the role of CRY1 in regulating Fv/Fm in cry1 mutants. Overall, the results of this research provide valuable insights into the unique role of each photoreceptor and their interplay in balancing photon energy and photoprotection under HL condition.


Subject(s)
Light , Photosystem II Protein Complex , Solanum lycopersicum , Solanum lycopersicum/genetics , Solanum lycopersicum/physiology , Solanum lycopersicum/radiation effects , Solanum lycopersicum/metabolism , Photosystem II Protein Complex/metabolism , Photosystem II Protein Complex/genetics , Photosynthesis/physiology , Phytochrome B/metabolism , Phytochrome B/genetics , Photoreceptors, Plant/metabolism , Photoreceptors, Plant/genetics , Mutation , Plant Proteins/genetics , Plant Proteins/metabolism , Phytochrome A/metabolism , Phytochrome A/genetics
7.
Nano Lett ; 24(7): 2250-2256, 2024 Feb 21.
Article in English | MEDLINE | ID: mdl-38329289

ABSTRACT

Emergence of complex catalytic machinery via simple building blocks under non-equilibrium conditions can contribute toward the system level understanding of the extant biocatalytic reaction network that fuels metabolism. Herein, we report temporal (dis)assembly of peptide nanostructures in presence of a cofactor dictated by native multistep cascade transformations. The short peptide can form a dynamic covalent bond with the thermodynamically activated substrate and recruit cofactor hemin to access non-equilibrium catalytic nanostructures (positive feedback). The neighboring imidazole and hemin moieties in the assembled state rapidly converted the substrate to product(s) via a two-step cascade reaction (hydrolase-peroxidase like) that subsequently triggered the disassembly of the catalytic nanostructures (negative feedback). The feedback coupled reaction cycle involving intrinsic catalytic prowess of short peptides to realize the advanced trait of two-stage cascade degradation of a thermodynamically activated substrate foreshadows the complex non-equilibrium protometabolic networks that might have preceded the chemical emergence of life.


Subject(s)
Hemin , Nanostructures , Hemin/chemistry , Nanostructures/chemistry , Peptides/chemistry , Catalysis , Biocatalysis
8.
Nano Lett ; 24(4): 1130-1136, 2024 Jan 31.
Article in English | MEDLINE | ID: mdl-38252698

ABSTRACT

Due to the coupled contributions of adhesion and carrier to friction typically found in previous research, decoupling the electron-based dissipation is a long-standing challenge in tribology. In this study, by designing and integrating a graphene/h-BN/graphene/h-BN stacking device into an atomic force microscopy, the carrier density dependent frictional behavior of a single-asperity sliding on graphene is unambiguously revealed by applying an external back-gate voltage, while maintaining the adhesion unaffected. Our experiments reveal that friction on the graphene increases monotonically with the increase of carrier density. By adjusting the back-gate voltage, the carrier density of the top graphene layer can be tuned from -3.9 × 1012 to 3.5 × 1012 cm-2, resulting in a ∼28% increase in friction. The mechanism is uncovered from the consistent dependence of the charge density redistribution and sliding barrier on the carrier density. These findings offer new perspectives on the fundamental understanding and regulation of friction at van der Waals interfaces.

9.
J Cell Physiol ; 239(2): e31165, 2024 Feb.
Article in English | MEDLINE | ID: mdl-38149820

ABSTRACT

Transforming growth factor (TGF)-ß1 is a multifunctional cytokine that plays important roles in health and disease. Previous studies have revealed that TGFß1 activation, signaling, and downstream cell responses including epithelial-mesenchymal transition (EMT) and apoptosis are regulated by the elasticity or stiffness of the extracellular matrix. However, tissues within the body are not purely elastic, rather they are viscoelastic. How matrix viscoelasticity impacts cell fate decisions downstream of TGFß1 remains unknown. Here, we synthesized polyacrylamide hydrogels that mimic the viscoelastic properties of breast tumor tissue. We found that increasing matrix viscous dissipation reduces TGFß1-induced cell spreading, F-actin stress fiber formation, and EMT-associated gene expression changes, and promotes TGFß1-induced apoptosis in mammary epithelial cells. Furthermore, TGFß1-induced expression of integrin linked kinase (ILK) and colocalization of ILK with vinculin at cell adhesions is attenuated in mammary epithelial cells cultured on viscoelastic substrata in comparison to cells cultured on nearly elastic substrata. Overexpression of ILK promotes TGFß1-induced EMT and reduces apoptosis in cells cultured on viscoelastic substrata, suggesting that ILK plays an important role in regulating cell fate downstream of TGFß1 in response to matrix viscoelasticity.


Subject(s)
Extracellular Matrix , Signal Transduction , Epithelial Cells/metabolism , Epithelial-Mesenchymal Transition , Extracellular Matrix/metabolism , Integrins/metabolism , Transforming Growth Factor beta1/pharmacology , Transforming Growth Factor beta1/metabolism , Animals , Mice , Cell Line , Elasticity , Viscosity
10.
Pflugers Arch ; 476(3): 365-377, 2024 Mar.
Article in English | MEDLINE | ID: mdl-38308122

ABSTRACT

To assess the influence of physical training on neuronal activation and hypothalamic expression of vasopressin and oxytocin in spontaneously hypertensive rats (SHR), untrained and trained normotensive rats and SHR were submitted to running until fatigue while internal body and tail temperatures were recorded. Hypothalamic c-Fos expression was evaluated in thermoregulatory centers such as the median preoptic nucleus (MnPO), medial preoptic nucleus (mPOA), paraventricular nucleus of the hypothalamus (PVN), and supraoptic nucleus (SON). The PVN and the SON were also investigated for vasopressin and oxytocin expressions. Although exercise training improved the workload performed by the animals, it was reduced in SHR and followed by increased internal body temperature due to tail vasodilation deficit. Physical training enhanced c-Fos expression in the MnPO, mPOA, and PVN of both strains, and these responses were attenuated in SHR. Vasopressin immunoreactivity in the PVN was also increased by physical training to a lesser extent in SHR. The already-reduced oxytocin expression in the PVN of SHR was increased in response to physical training. Within the SON, neuronal activation and the expressions of vasopressin and oxytocin were reduced by hypertension and unaffected by physical training. The data indicate that physical training counterbalances in part the negative effect of hypertension on hypothalamic neuronal activation elicited by exercise, as well as on the expression of vasopressin and oxytocin. These hypertension features seem to negatively influence the workload performed by SHR due to the hyperthermia derived from the inability of physical training to improve heat dissipation through skin vasodilation.


Subject(s)
Hypertension , Running , Rats , Animals , Rats, Inbred SHR , Oxytocin/metabolism , Oxytocin/pharmacology , Hypothalamus/metabolism , Paraventricular Hypothalamic Nucleus/metabolism , Vasopressins/metabolism , Hypertension/metabolism , Fatigue
11.
Small ; 20(35): e2401622, 2024 Aug.
Article in English | MEDLINE | ID: mdl-38682610

ABSTRACT

Single-network hydrogels are often too fragile to withstand mechanical loading, whereas double-network hydrogels typically exhibit significant hysteresis during cyclic stretching-releasing process due to the presence of a sacrificial network. Consequently, it is a considerable challenge for designing hydrogels that are both low in hysteresis and high in toughness for applications requiring dynamic mechanical loads. Herein, the study introduced a novel "sliding tangle island" strategy for creating tough and low-hysteresis hydrogels, which are prepared through in situ polymerization of highly concentrated acrylamides (AM) to form numerous entanglements within the MXene spacing without any chemical crosslinker. The MXene entangled with long polyacrylamide (PAM) chains to form tangle island that served as a relay station to transmit stress to neighboring molecular chains. This mechanism helps alleviate stress concentration and enhances energy dissipation efficiency, thereby reducing mechanical hysteresis. The resulting hydrogel exhibited exceptional properties, including high stretchability (≈900%), low hysteresis (less than 7%), high toughness (1.34 MJ m-3), and excellent sensing performance to rival the commercial hydrogel electrode. Therefore, this work sheds light on feasible design of energy dissipation structure to reduce the hysteresis of the composite hydrogels.

12.
Small ; : e2403040, 2024 Jul 10.
Article in English | MEDLINE | ID: mdl-38984759

ABSTRACT

Superspreading surfaces with excellent water transport efficiency are highly desirable for addressing thermal failures through the liquid-vapor phase change of water in electronics thermal management applications. However, the trade-off between capillary pressure and viscous resistance in traditional superspreading surfaces with micro/ nanostructures poses a longstanding challenge in the development of superspreading surfaces with high cooling efficiency in confined spaces. Herein, a heat-treated hierarchical porous enhanced superspreading surface (HTHP) for highly efficient electronic cooling is proposed. Compared with the single porous structures in nanograss, nanosheets, and copper foam, HTHP with hierarchical honeycomb pores effectively resolves the trade-off effect by introducing large vertical through-pores to reduce viscous resistance, and connected small pores to provide sufficient capillary pressure synergistically. HTHP exhibits excellent capillary performance in both horizontal spreading and vertical rising. Despite a thickness of only 0.33 mm, the as-prepared ultrathin vapor chamber (UTVC) fabricated to exploit the superior capillary performance of HTHP achieved effective heat dissipation with outstanding thermal conductivity (12 121 Wm-1K-1), and low thermal resistance (0.1 KW-1) at a power of 5 W. This regulation strategy based on hierarchical honeycomb porous structures is expected to promote the development of high-performance superspreading surfaces with a wide range of applications in thermal management.

13.
Small ; : e2404556, 2024 Jul 19.
Article in English | MEDLINE | ID: mdl-39032001

ABSTRACT

Silicon (Si) is a promising anode material for high-energy-density lithium-ion batteries, but the significant volume change of Si particles during alloying/dealloying with lithium (Li) undermines the mechanical integrity of Si anode, causing electrode fracture, delamination and rapid capacity decay. Herein, a robust triple crosslinked network (TCN) binder with high ionic conductivity and hierarchical stress dissipation is reported for Si anodes, which is prepared by in situ chemical crosslinking polyacrylic acid (PAA) and melamine (MA). The triple interactions of hydrogen bonds, electrostatic interactions, and covalent amide bonds enhance the adhesion of binder to Si and synergistically promote stress dissipation within Si anodes, thus strengthening the dynamic structural stability of Si anodes during cycling. Moreover, the rapid coupling/decoupling of Li+ with the TCN binder enables an impressive Li+ transference number of 0.63 and high ionic conductivity of 1.2 × 10-4 S cm-1. Consequently, the Si-TCN anode delivers specific capacity of 2268 mAh g-1 with a high mass loading of 2 mg cm-2, high-rate performance of 1673 mAh g-1 at 5 A g-1, and stable cycling for 250 cycles at 1 A g-1, thus showing great prospects for high-energy-density Si-based batteries.

14.
Small ; 20(38): e2401573, 2024 Sep.
Article in English | MEDLINE | ID: mdl-38773876

ABSTRACT

2D transition metal borides, known as MBenes, have attracted considerable attention due to their exceptional properties. This study explores the feasibility of aluminum (Al) etching from MoAlB using environmentally friendly and sustainable fluoride-free dilute acidic/alkaline solutions at room temperature, revealing its thermodynamic and kinetic viability. Furthermore, it is found that complete removal of Al can be achieved in dilute alkaline reagent under hydrothermal conditions, yielding pristine single/few-layered MBene-MoB for the first time, while acidic solutions result in ≈33% etching rates. XRD refinement, which tracks aluminum removal from 0% to 100%, reveals transient metastable phases of MoAl1-xB (x < 0.5) in the initial etching stages, evolving into relatively stable pure Mo2AlB2 structures with 50% Al deficiency, serving as a precursor to MBenes. The subsequent loss of Al results in a 2D MBene-MoB structure. DFT calculations confirm excellent conductivity for MoAlB, MoAl1-xB (x = 0-1), and MBene-MoB. Remarkably, MBene-MoB exhibits superior supercapacitor performance with a 4025.60 mF cm-2/201.28 F g-1 capacitance. Simulations validate rapid electrolyte diffusion in layered MBene-MoB, contributing significantly to enhanced capacitance. Additionally, in the hydrogen evolution reaction (HER), MBene-MoB demonstrates superior catalytic activity compared to the precursor MoAlB and commercial MoB. Calculations suggest the potential for enhancing HER through surface modulation, considering its suboptimal hydrogen adsorption energy.

15.
Small ; 20(35): e2400115, 2024 Aug.
Article in English | MEDLINE | ID: mdl-38678491

ABSTRACT

High-power-density electronic devices under vibrations call for soft and damping thermal interface materials (TIMs) for efficient heat dissipation. However, integrating low hardness, high damping, and superior heat transfer capability into one TIM is highly challenging. Herein, soft, damping, and thermally conductive TIMs are designed and prepared by constructing a honeycomb-board-mimetic boron nitride nanosheet (BNNS) network in a dynamic polyimine via one-step horizontal centrifugal casting. The unique filler network makes the TIMs perform a high through-plane thermal conductivity (> 7.69 W m-1 K-1) and a uniform heat transfer process. Meanwhile, the hierarchical dynamic bonding of the polyimine endows the TIMs with low compressive strength (2.16 MPa at 20% strain) and excellent damping performance (tan δ > ≈0.3 at 10-2-102 Hz). The resulting TIMs also exhibit electrical insulation and remarkable recycling ability. Compared with the commercial ones, the TIMs provide better heat dissipation (4.1 °C) for a high-power 5G base station and less temperature fluctuation (1.8 °C) for an automotive insulated gate bipolar transistor (IGBT) under vibrations. This rational design offers a viable approach to prepare soft and damping TIMs for effective heat dissipation of high-power-density electronic devices under vibrations.

16.
Small ; 20(13): e2305574, 2024 Mar.
Article in English | MEDLINE | ID: mdl-37964293

ABSTRACT

Thermal management is critical in contemporary electronic systems, and integrating diamond with semiconductors offers the most promising solution to improve heat dissipation. However, developing a technique that can fully exploit the high thermal conductivity of diamond, withstand high-temperature annealing processes, and enable mass production is a significant challenge. In this study, the successful transfer of AlGaN/GaN/3C-SiC layers grown on Si to a large-size diamond substrate is demonstrated, followed by the fabrication of GaN high electron mobility transistors (HEMTs) on the diamond. Notably, no exfoliation of 3C-SiC/diamond bonding interfaces is observed even after annealing at 1100 °C, which is essential for high-quality GaN crystal growth on the diamond. The thermal boundary conductance of the 3C-SiC-diamond interface reaches ≈55 MW m-2 K-1, which is efficient for device cooling. GaN HEMTs fabricated on the diamond substrate exhibit the highest maximum drain current and the lowest surface temperature compared to those on Si and SiC substrates. Furthermore, the device thermal resistance of GaN HEMTs on the diamond substrate is significantly reduced compared to those on SiC substrates. These results indicate that the GaN/3C-SiC on diamond technique has the potential to revolutionize the development of power and radio-frequency electronics with improved thermal management capabilities.

17.
Photosynth Res ; 160(1): 17-29, 2024 Apr.
Article in English | MEDLINE | ID: mdl-38407779

ABSTRACT

Phycobilisomes (PBs) play an important role in cyanobacterial photosynthesis. They capture light and transfer excitation energy to the photosynthetic reaction centres. PBs are also central to some photoprotective and photoregulatory mechanisms that help sustain photosynthesis under non-optimal conditions. Amongst the mechanisms involved in excitation energy dissipation that are activated in response to excessive illumination is a recently discovered light-induced mechanism that is intrinsic to PBs and has been the least studied. Here, we used single-molecule spectroscopy and developed robust data analysis methods to explore the role of a terminal emitter subunit, ApcE, in this intrinsic, light-induced mechanism. We isolated the PBs from WT Synechocystis PCC 6803 as well as from the ApcE-C190S mutant of this strain and compared the dynamics of their fluorescence emission. PBs isolated from the mutant (i.e., ApcE-C190S-PBs), despite not binding some of the red-shifted pigments in the complex, showed similar global emission dynamics to WT-PBs. However, a detailed analysis of dynamics in the core revealed that the ApcE-C190S-PBs are less likely than WT-PBs to enter quenched states under illumination but still fully capable of doing so. This result points to an important but not exclusive role of the ApcE pigments in the light-induced intrinsic excitation energy dissipation mechanism in PBs.


Subject(s)
Photosynthetic Reaction Center Complex Proteins , Synechocystis , Phycobilisomes/metabolism , Synechocystis/metabolism , Photosynthetic Reaction Center Complex Proteins/metabolism , Bacterial Proteins/metabolism , Spectrometry, Fluorescence
18.
Chemphyschem ; 25(14): e202400246, 2024 Jul 15.
Article in English | MEDLINE | ID: mdl-38656666

ABSTRACT

In MLCT chromophores, internal conversion (IC) in the form of hole reconfiguration pathways (HR) is a major source of dissipation of the absorbed photon energy. Therefore, it is desirable to minimize their impact in energy conversion schemes by slowing them down. According to previous findings on {Ru(bpy)} chromophores, donor-acceptor interactions between the Ru ion and the ligand scaffold might allow to control HR/IC rates. Here, a series of [Ru(tpm)(bpy)(R-py)]2+ chromophores, where tpm is tris(1-pyrazolyl)methane, bpy is 2,2'-bipyridine and R-py is a 4-substituted pyridine, were prepared and fully characterized employing electrochemistry, spectroelectrochemistry, steady-state absorption/emission spectroscopy and electronic structure computations based on DFT/TD-DFT. Their excited-state decay was monitored using nanosecond and femtosecond transient absorption spectroscopy. HR/IC lifetimes as slow as 568 ps were obtained in DMSO at room temperature, twice as slow as in the reference species [Ru(tpm)(bpy)(NCS)]+.

19.
J Exp Biol ; 227(4)2024 02 15.
Article in English | MEDLINE | ID: mdl-38264846

ABSTRACT

According to the heat dissipation limit (HDL) theory, reproductive performance is limited by the capacity to dissipate excess heat. We tested the novel hypotheses that (1) the age-related decline in reproductive performance is due to an age-related decrease of heat dissipation capacity and (2) the limiting mechanism is more severe in animals with high metabolic rates. We used bank voles (Myodes glareolus) from lines selected for high swim-induced aerobic metabolic rate, which have also increased basal metabolic rate, and unselected control lines. Adult females from three age classes - young (4 months), middle-aged (9 months) and old (16 months) - were maintained at room temperature (20°C), and half of the lactating females were shaved to increase heat dissipation capacity. Old females from both selection lines had a decreased litter size, mass and growth rate. The peak-lactation average daily metabolic rate was higher in shaved than in unshaved mothers, and this difference was more profound among old than young and middle-aged voles (P=0.02). In females with large litters, milk production tended to be higher in shaved (least squares mean, LSM±s.e.: 73.0±4.74 kJ day-1) than in unshaved voles (61.8±4.78 kJ day-1; P=0.05), but there was no significan"t effect of fur removal on the growth rate [4.47±2.29 g (4 days-1); P=0.45]. The results provide mixed support of the HDL theory and no support for the hypotheses linking the differences in reproductive aging with either a deterioration in thermoregulatory capability or genetically based differences in metabolic rate.


Subject(s)
Hot Temperature , Lactation , Animals , Female , Energy Intake , Arvicolinae , Aging , Energy Metabolism
20.
J Theor Biol ; 595: 111933, 2024 Sep 10.
Article in English | MEDLINE | ID: mdl-39260737

ABSTRACT

We report the effects of varying physiological and other properties on the heat and water exchange in the maxilloturbinate structure (MT) of the bearded seal (Erignathus barbatus or Eb) in realistic environments, using a computational fluid dynamics (CFD) model. We find that the water retention in percent is very high (about 90 %) and relatively unaffected by either cold (-30 °C) or warm (10 °C) conditions. The retention of heat is also high, around 80 % . Based on a consideration of entropy production by the maxilloturbinate system, we show that anatomical and physiological properties of the seal provide good conditions for heat and water exchange at the mucus lining in the seal's nasal cavity. At normal values of tidal volume and maxilloturbinate (MT) length, the air temperature in the MT reaches the body temperature before the air has left the MT channels. This confers a safety factor which is expected to be helpful in exercise, when ventilation increases.

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