Perturbation Of State Research Articles

Massively parallel Hong-Ou-Mandel interference based on independent soliton microcombs.

Hong-Ou-Mandel (HOM) interference is the foundation of quantum optics to test the degree of indistinguishability of two incoming photons, playing a key role in quantum communication, sensing, and photonic quantum computing. Realizing high-visibility HOM interference with massively parallel optical channels is challenging due to the lack of available natural optical references for aligning independent arrayed laser pairs. Here, we demonstrate 50 parallel comb-teeth pairs of continuous-wave weak coherent photons HOM interference using two independently frequency post-aligned soliton microcombs (SMCs), achieving an average fringe visibility over 46%. The frequencies of all comb-teeth pairs are long-term aligned by developing two sets of fully frequency-stabilized SMCs with independent reference and adjusting free spectral range beyond 100 kilohertz through perturbations in soliton state. The verification experiment proves the feasibility of constructing massively quantum information channels by co-opting classical wavelength division multiplexing optical communications, which paves the way for practical large-scale quantum communication systems.

A multi-omics spatial framework for host-microbiome dissection within the intestinal tissue microenvironment

The intricate interactions between the host immune system and its microbiome constituents undergo dynamic shifts in response to perturbations to the intestinal tissue environment. Our ability to study these events on the systems level is significantly limited by in situ approaches capable of generating simultaneous insights from both host and microbial communities. Here, we introduce Microbiome Cartography (MicroCart), a framework for simultaneous in situ probing of host and microbiome across multiple spatial modalities. We demonstrate MicroCart by investigating gut host and microbiome changes in a murine colitis model, using spatial proteomics, transcriptomics, and glycomics. Our findings reveal a global but systematic transformation in tissue immune responses, encompassing tissue-level remodeling in response to host immune and epithelial cell state perturbations, bacterial population shifts, localized inflammatory responses, and metabolic process alterations during colitis. MicroCart enables a deep investigation of the intricate interplay between the host tissue and its microbiome with spatial multi-omics.

Extended Active Space Ab Initio Ligand Field Theory: Applications to Transition-Metal Ions.

Ligand field theory (LFT) is one of the cornerstones of coordination chemistry since it provides a conceptual framework in which a great many properties of d- and f-element compounds can be discussed. While LFT serves as a powerful qualitative guide, it is not a tool for quantitative predictions on individual compounds since it incorporates semiempirical parameters that must be fitted to experiment. One way to connect the realms of first-principles electronic structure theory that has emerged as particularly powerful over the past decade is the ab initio ligand field theory (AILFT). The original formulation of this method involved the extraction of LFT parameters by fitting the ligand field Hamiltonian to a complete active space self-consistent field (CASSCF) Hamiltonian. The extraction was shown to be unique provided that the active space consists of 5/7 metal d/f-based molecular orbitals (MOs). Subsequent improvements have involved incorporating dynamical correlation using second-order N-electron valence state perturbation theory (NEVPT2) or second-order dynamical correlation dressed complete active space (DCDCAS). However, the limitation of past approaches is that the method requires a minimal space of 5/7 metal d- or f-based molecular orbitals. This leads to a number of limitations: (1) neglect of radial or semicore correlation would arise from the effect of a second d-shell or an sp-shell in the active space, (2) a more balanced description of metal-ligand bond covalency is lacking because the bonding ligand-based counterparts of the metal d/f orbitals are not in the active space. This usually leads to an exaggerated ionicity of the M-L bonds. In this work, we present an extended active space AILFT (esAILFT) that circumvents these limitations and is, in principle, applicable to arbitrary active spaces, as long as these contain the 5/7 metal d/f-based MOs as a subset. esAILFT was implemented in a development version of the ORCA software package. In order to help with the application of the new method, various criteria for active space extension were explored for 3d, 4d, and 5d transition-metal ions with varying charge. An interpretation of the trends in the Racah B parameter for these ions is also presented as a demonstration of the capabilities of esAILFT.

The biliary ecosystem: a holistic perspective on critical scientific issues regarding biliary tract surgeries and diseases

The establishment of modern biliary surgery system, alongside pivotal scientific paradigm shifts, has heralded a new era featured by precision, personalization, life-cycle care, and multidisciplinary management in the treatment of both benign and malignant biliary diseases. However, two formidable challenges persist in haunting the treatment of biliary diseases: (1) The refinement of surgical techniques has reached a plateau in reducing the disability associated with benign biliary conditions and in improving survival outcomes in biliary tract cancers; (2) Traditional evidence-based clinical studies have shown limited power in addressing complex dilemmas, such as determining whether to excise or preserve pathological gallbladders or selecting the optimal biliary drainage strategy. Consequently, the authors propose the conceptual framework of "biliary ecosystem". In this model, diverse and abundant cholangiocytes represent forest, while blood vessels, nerves, and lymphatic vessels serve as nurturing soil, biliary stem cells function as seeds, bile flows like river network, and hepatocytes mark the river's origins. Both benign and malignant biliary diseases exhibit significant spatiotemporal dynamics. The bile ducts form the "macro" environment, bile constitutes the "sub-macro" environment, and diverse cellular niches create the microenvironment. Specific pathological biliary conditions are shaped by intricate regulatory mechanisms that operate across these three tiers. Within the biliary ecosystem, cellular subpopulations exist remarkable diversity with states of homeostasis, oscillation, perturbation, or imbalance, underpinned by complex signaling networks. This holistic approach allows us to reframe and critically examine the pressing scientific issues confronting biliary tract diseases. Based on this framework, the authors distill key scientific questions and offer preliminary recommendations for embracing the paradigm shift. The authors anticipate that this conceptual model will promote interdisciplinary integration and accelerate clinical and translational researches.

Importance of Electron Correlation on the Geometry and Electronic Structure of [2Fe-2S] Systems: A Benchmark Study of the [Fe2S2(SCH3)4]2-,3-,4-, [Fe2S2(SCys)4]2-, [Fe2S2(S-p-tol)4]2-, and [Fe2S2(S-o-xyl)4]2- Complexes.

Iron-sulfur clusters are crucial for biological electron transport and catalysis. Obtaining accurate geometries, energetics, manifolds of their excited electronic states, and reduction energies is important to understand their role in these processes. Using a [2Fe-2S] model complex with FeII and FeIII oxidation states, which leads to different charges, i.e., [Fe2S2(SMe)4]2-,3-,4-, we benchmarked a variety of computational methodologies ranging from density functional theory (DFT) to post-Hartree-Fock methods, including complete active space self-consistent field (CASSCF), multireference configuration interaction, the second-order N-electron valence state perturbation theory (NEVPT2), and the linearized integrand approximation of adiabatic connection (AC0) approaches. Additionally, we studied three experimentally well-characterized complexes, [Fe2S2(SCys)4]2-, [Fe2S2(S-o-tol)4]2-, and [Fe2S2(S-o-xyl)4]2-, via DFT methods. We conclude that the dynamic electron correlation is important for accurately predicting the geometry of these complexes. Broken symmetry (BS) DFT correctly predicts experimental geometries of low-spin multiplicity, while CASSCF does not. However, BS-DFT significantly overestimates the difference between the low- and high-spin electronic states for a given oxidation state. At the same time, CASSCF underestimates it but provides relative energies closer to the reference NEVPT2 results. Finally, AC0 provides energetics of NEVPT2 quality with the additional advantage of being able to use large CASSCF sizes. NEVPT2 gives the best estimates of the FeIII/FeIII → FeII/FeIII (4.27 eV) and FeII/FIII → FeII/FII (7.72 eV) reduction energies. The results provide insight into the electronic structure of these complexes and assist in the understanding of their physical properties.

Relative State Counting for Semiclassical Black Holes.

It has been shown that entropy differences between certain states of perturbative quantum gravity can be computed without specifying an ultraviolet completion. This is analogous to the situation in classical statistical mechanics, where entropy differences are defined but absolute entropy is not. Unlike in classical statistical mechanics, however, the entropy differences computed in perturbative quantum gravity do not have a clear physical interpretation. Here we construct a family of perturbative black hole states for which the entropy difference can be interpreted as a relative counting of states. Conceptually, this Letter begins with the algebra of mass fluctuations around a fixed black hole background, and points out that while this is a type I algebra, it is not a factor and therefore has no canonical definition of entropy. As in previous work, coupling the mass fluctuations to quantum matter embeds the mass algebra within a type II factor, in which entropy differences (but not absolute entropies) are well defined. It is then shown that for microcanonical wave functions of mass fluctuation, the type II entropy difference equals the logarithm of the dimension of the extra Hilbert space that is needed to map one microcanonical window to another using gauge-invariant unitaries. The Letter closes with comments on type II entropy difference in a more general class of states, where the von Neumann entropy difference does not have a physical interpretation, but "one-shot" entropy differences do.

Existence and stability of almost finite energy weak solutions to the quantum Euler-Maxwell system

In this paper we prove the existence of global in time, finite energy weak solutions to the quantum magnetohydrodynamics (QMHD) system, for a large class of initial data that are slightly more regular than being of finite energy. No restriction is given on their size or the uniform positivity of the mass density. The QMHD system is a well-established model in superconductivity due to Feynman, and is intimately related to a nonlinear Maxwell-Schrödinger (NLMS) system via the Madelung transformations. The lack of global well-posedness (GWP) results for the NLMS system in the energy norm provides an obstruction to stability of its solutions, and consequently to the use of approximation arguments to make rigorous the Madelung approach. We implement here a new strategy, that derives weak solutions to QMHD starting from weak solutions to NLMS, by exploiting its Duhamel formulation. This derivation is rigorously justified by means of suitable dispersive/smoothing estimates for almost finite energy weak solutions to NLMS. The corresponding weak solutions to QMHD satisfy a generalized irrotationality condition, that allows for the presence of non-trivial vorticity (e.g., vortex filaments) concentrated in the vacuum region. This is in sharp contrast with the Euler-Maxwell system where the dispersion is not able to deal with the vorticity transport, therefore almost GWP (for regular solutions that are small perturbations of constant states) holds only in a lifespan, reciprocal of the size of the initial vorticity. Moreover, we also prove a stability property in the energy norm of the weak solutions constructed by our approach. This result follows from new local smoothing estimates for NLMS that are also of independent interest. As a byproduct, we also show the stability for the electromagnetic Lorentz force.

Nonlinear model predictive dynamic positioning of a remotely operated vehicle with wave disturbance preview

Exploiting preview information of disturbances within robot control is an effective method of handling state perturbations. For underwater vehicles operating in wave-dominated environments, disturbances significantly influence vehicle response and pose a threat to operational safety. In consideration of this, a complete end-to-end control architecture is developed in this work for disturbance rejection during station keeping tasks under wave perturbations, encompassing a nonlinear model predictive controller (NMPC) combined with a deterministic sea wave predictor (DSWP). The wave predictor exploits a continuous measurement of the wave elevation at a location upstream of the vehicle to form a forecast of the temporal evolution of the wave elevation at the vehicle location. The predicted wave parameters are then used to estimate the impending wave-induced hydrodynamic loading, enabling explicit consideration of accurate short-term disturbance forecasts within the controller, ensuring this preview is incorporated in the optimised control sequence. Experimental testing confirms the validity of the wave predictor, producing RMSE as low as 0.017 m. The proposed strategy is then simulated under various wave conditions, optimising control actions inclusive of the preview information. The NMPC outperforms a similar disturbance mitigating feed-forward controller, with average improvements of up to 52% and is found to perform best even with noisy, lower accuracy wave predictions, as well as with communication time delays, providing a high degree of robustness. This demonstrates the potential of the proposed control framework to effectively tackle disturbance mitigation of underwater vehicles subject to large magnitude wave disturbances, expanding the operational envelop of autonomous systems towards forbidding ocean environments.

Interacting myosin head dynamics and their modification by 2′-deoxy-ADP

The contraction of striated muscle is driven by cycling myosin motor proteins embedded within the thick filaments of sarcomeres. In addition to cross-bridge cycling with actin, these myosin proteins can enter an inactive, sequestered state in which the globular S1 heads rest along the thick filament surface and are inhibited from performing motor activities. Structurally, this state is called the interacting heads motif (IHM) and is a critical conformational state of myosin that regulates muscle contractility and energy expenditure. Structural perturbation of the sequestered state can pathologically disrupt IHM structure and the mechanical performance of muscle tissue. Thus, the IHM state has become a target for therapeutic intervention. An ATP analog called 2′-deoxy-ATP (dATP) is a potent myosin activator that destabilizes the IHM. Here, we use molecular dynamics simulations to study the molecular mechanisms by which dATP modifies the structure and dynamics of myosin in a sequestered state. Simulations of the IHM state containing ADP.Pi in both nucleotide binding pockets revealed dynamic motions of the blocked head-free head interface, light chain binding domain, and S2 in this “inactive” state of myosin. Replacement of ADP.Pi by dADP.Pi triggered a series of structural changes that increased heterogeneity among residue contact pairs at the blocked head-free head interface and a 14% decrease in the interaction energy at the interface. Dynamic changes to this interface were accompanied by dynamics in the light chain binding region. A comparative analysis of these dynamics predicted new structural sites that may affect IHM stability.

Sorption of PFOS onto polystyrene microplastics potentiates synergistic toxic effects during zebrafish embryogenesis and neurodevelopment

Microplastics (MPs) have become an emerging anthropogenic pollutant, and their ability to sorb contaminants potentially enhances the threats to the ecosystem. Only a few studies are available to understand the combined effects of microplastics and other pollutants. The present study investigated the sorption of perfluorooctane sulfonic acid (PFOS) onto polystyrene microplastics (PS-MPs) at varying concentrations, using molecular dynamics simulation (MDS) to preliminarily explore the adsorption behavior. The MDS results revealed negative interaction energies between PFOS and PS-MPs, underscoring PS-MPs' role as a potential adsorbent for PFOS in an aqueous solution. Thereafter, zebrafish embryos were employed to explore the toxic effects of combined exposure to PS-MPs and PFOS. Fluorescence and Scanning Electron Microscopy (SEM) suggested PS-MP accumulation individually and in combination with PFOS on the embryonic chorion membrane. As a result, the exposed group showed increased inner pore size of the chorionic membrane and accelerated heartbeat, indicating hypoxic conditions and hindered gaseous exchange. PS-MPs aggravated the toxicity of PFOS during larval development manifested by delayed hatching rate, increased mortality, and malformation rate. Additionally, increased ROS accumulation and altered antioxidant enzymatic status were observed in all the exposed groups suggesting perturbation of the redox state. Additionally, co-exposure of zebrafish larvae to PS-MPs and PFOS resulted in an abrupt behavioral response, which decreased AChE activity and altered neurotransmitter levels. Taken together, our results emphasize that PS-MPs can act as a potential vector for PFOS, exerting synergistic toxic effects in the aquatic environment, and hence their health risks cannot be ignored.

Extended Neighboring Extremal Optimal Control With State and Preview Perturbations

Extended Neighboring Extremal Optimal Control With State and Preview Perturbations

A Robust Mean-Field Actor-Critic Reinforcement Learning Against Adversarial Perturbations on Agent States.

Multiagent deep reinforcement learning (DRL) makes optimal decisions dependent on system states observed by agents, but any uncertainty on the observations may mislead agents to take wrong actions. The mean-field actor-critic (MFAC) reinforcement learning is well-known in the multiagent field since it can effectively handle a scalability problem. However, it is sensitive to state perturbations that can significantly degrade the team rewards. This work proposes a Robust MFAC (RoMFAC) reinforcement learning that has two innovations: 1) a new objective function of training actors, composed of a policy gradient function that is related to the expected cumulative discount reward on sampled clean states and an action loss function that represents the difference between actions taken on clean and adversarial states and 2) a repetitive regularization of the action loss, ensuring the trained actors to obtain excellent performance. Furthermore, this work proposes a game model named a state-adversarial stochastic game (SASG). Despite the Nash equilibrium of SASG may not exist, adversarial perturbations to states in the RoMFAC are proven to be defensible based on SASG. Experimental results show that RoMFAC is robust against adversarial perturbations while maintaining its competitive performance in environments without perturbations.

Evidence for landslides in Sisyphi Cavi (Noachis Terra, Mars): Slope evolution and role of endogenous preparatory factors

The surface of Mars is characterized by the presence of numerous gravity-induced processes and mass movements with greatly variable sizes and peculiarities. Detailed geomorphological studies have recently made it possible to identify many landslide-like landforms along the slopes bordering pits of Sisyphi Cavi in Noachis Terra, the southern hemisphere of Mars. These pieces of evidence are generally characterized by extended trenches, sometimes associated with uphill- or downhill-facing scarps. In this study, the gravity-induced processes observed in this region of Mars, and especially those present in a closed pit of the eastern sector, are described for the first time. A quantitative stress-strain analysis was performed, and it excludes a type of deformation process that could invoke creep processes (“viscosity-driven”) but rather favors instability induced by stress-perturbations in the slope more concentrated over time (“force-driven”). In particular, we performed a parametric analysis on both viscosity and stiffness parameters of the materials involved. It demonstrates that the time necessary for the rheological evolution of deformational processes associated with the observed landforms are compatible with genesis of short-term instabilities. This finding has significant implications for the origin of the depressed forms within and close to the study area, which are characterized by unstable slopes present at their edges. It is therefore not necessary to invoke the role of “viscosity-driven” creep processes to explain the origin of the shapes associated with the observed gravity-induced slope instabilities. The reported results drive towards a new interpretative scenario of morphological evolution of the widespread pits in the study area in terms of efficiency of endogenous processes (such as hypabyssal magmatism) which characterize the studied area of Mars, even if it is not possible to exclude the role of exogenous processes.

Regulating Functional Groups to Construct a Mild Passivator Enhancing the Efficiency and Stability of Carbon-Based Perovskite Solar Cells.

The abundant defects on the perovskite surface greatly impact the efficiency improvement and long-term stability of carbon-based perovskite solar cells. Molecules with electron-donating or electron-withdrawing functional groups have been cited for passivating various defects. However, few studies have investigated the potential adverse effects arising from the synergistic interactions among functional groups. Herein, we investigate the correlation between functional group configurations and passivation strength as well as the potential adverse impacts of strong electrostatic structures by methodically designing three distinct interface molecules functionalized with different ending groups, which both belong to biguanide derivatives, including 1-(3,4-dichlorophenyl) biguanide hydrochloride (DBGCl), metformin hydrochloride (MFCl), and biguanide hydrochloride (BGCl). The results indicate that DBGCl establishes comparatively mild active sites, not only passivates defects but also aids in forming a surface with a uniform potential. Conversely, MFCl exerts a more pronounced adverse effect on the perovskite surface, which is attributable to the electronic state perturbations induced by its functional groups. Due to the lack of hydrophobic groups, devices treated with BGCl demonstrate insufficient moisture resistance. Devices passivated with DBGCl demonstrate superior average efficiency, showcasing a 12% enhancement relative to the pristine. Furthermore, DBGCl-treated devices exhibit enhanced stability in three different environments, respectively, achieving the highest PCE retention rates under nitrogen conditions (25 °C), room-temperature air conditions (25 °C, RH = 40 ± 2%), and high-temperature air conditions (65 °C, RH = 40 ± 2%).

Combined Multireference-Multiscale Approach to the Description of Photosynthetic Reaction Centers.

A first-principles description of the primary photochemical processes that drive photosynthesis and sustain life on our planet remains one of the grand challenges of modern science. Recent research established that explicit incorporation of protein electrostatics in excited-state calculations of photosynthetic pigments, achieved for example with quantum-mechanics/molecular-mechanics (QM/MM) approaches, is essential for a meaningful description of the properties and function of pigment-protein complexes. Although time-dependent density functional theory has been used productively so far in QM/MM approaches for the study of such systems, this methodology has limitations. Here we pursue for the first time a QM/MM description of the reaction center in the principal enzyme of oxygenic photosynthesis, Photosystem II, using multireference wave function theory for the high-level QM region. We identify best practices and establish guidelines regarding the rational choice of active space and appropriate state-averaging for the efficient and reliable use of complete active space self-consistent field (CASSCF) and the N-electron valence state perturbation theory (NEVPT2) in the prediction of low-lying excited states of chlorophyll and pheophytin pigments. Given that the Gouterman orbitals are inadequate as a minimal active space, we define specific minimal and extended active spaces for the NEVPT2 description of electronic states that fall within the Q and B bands. Subsequently, we apply our multireference-QM/MM protocol to the description of all pigments in the reaction center of Photosystem II. The calculations reproduce the electrochromic shifts induced by the protein matrix and the ordering of site energies consistent with the identity of the primary donor (ChlD1) and the experimentally known asymmetric and directional electron transfer. The optimized protocol sets the stage for future multireference treatments of multiple pigments, and hence for multireference studies of charge separation, while it is transferable to the study of any photoactive embedded tetrapyrrole system.

A well-balanced finite volume solver for the 2D shallow water magnetohydrodynamic equations with topography

In this paper, a second-order finite volume Non-Homogeneous Riemann Solver is used to obtain an approximate solution for the two-dimensional shallow water magnetohydrodynamic (SWMHD) equations considering non-flat bottom topography. We investigate the stability of a perturbed steady state, as well as the stability of energy in these equations after a perturbation of a steady state using a dispersive analysis. To address the elliptic constraint ∇⋅hB=0, the GLM (Generalized Lagrange Multiplier) method designed specifically for finite volume schemes, is used. The proposed solver is implemented on unstructured meshes and verifies the exact conservation property. Several numerical results are presented to validate the high accuracy of our schemes, the well-balanced, and the ability to resolve smooth and discontinuous solutions. The developed finite volume Non-Homogeneous Riemann Solver and the GLM method offer a reliable approach for solving the SWMHD equations, preserving numerical and physical equilibrium, and ensuring stability in the presence of perturbations.

Well-posedness and decay structure of a quantum hydrodynamics system with Bohm potential and linear viscosity

In this paper, a compressible viscous-dispersive Euler system in one space dimension in the context of quantum hydrodynamics is considered. The purpose of this study is twofold. First, it is shown that the system is locally well-posed. For that purpose, the existence of classical solutions which are perturbation of constant states is established. Second, it is proved that in the particular case of subsonic equilibrium states, sufficiently small perturbations decay globally in time. In order to prove this stability property, the linearized system around the subsonic state is examined. Using an appropriately constructed compensating matrix symbol in the Fourier space, it is proved that solutions to the linear system decay globally in time, underlying a dissipative mechanism of regularity gain type. These linear decay estimates, together with the local existence result, imply the global existence and the decay of perturbations to constant subsonic equilibrium states as solutions to the full nonlinear system.

Five-dimensional Myers-Perry black holes under massive scalar perturbation: bound states and quasinormal modes

The stability of five-dimensional singly rotating Myers-Perry Black Holes against massive scalar perturbations is studied. Both the quasibound states and quasinormal modes of the massive scalar field are considered. For the quasibound states, we use an analytical method to discuss the effective potential felt by the scalar field, and found that there is no potential well outside the event horizon. Thus, singly rotating Myers-Perry Black Holes are stable against the perturbation of quasibound states of massive scalar fields. Then, we use continued fraction method based on solving a seven-term recurrence relations to compute the spectra of the quasinormal modes. For different values of the black hole rotation parameter a, scalar mass parameter μ and angular quantum numbers, all found quasinormal modes are damped. Besides, when the scalar mass μ becomes relatively large, the long-living quasiresonances are also found as in other rotating black hole models. Our results complement previous arguments on the stability of five-dimensional singly rotating Myers-Perry black holes against massive scalar perturbations.

Multireference Ab Initio Calculations on Excited Electronic States of Carbazole-Based Organic Compounds for Thermally Activated Delayed Fluorescence.

The emerging technology of organic light-emitting diodes takes advantage of the thermally activated delayed fluorescence (TADF) mechanism for improved efficiency. Carbazole-based organic molecules are suitable for TADF emission because of charge transfer excitations between the electron-donor carbazole and an electron-acceptor unit. Computational design of new TADF molecules with the desired properties is challenging because charge-transfer excitations cannot be predicted accurately by time-dependent density functional theory. Four groups of carbazole-based donor-acceptor molecules have been studied using multireference ab initio methods to understand the nature of excited electronic states. The state-averaged complete active space self-consistent field (SA-CASSCF) and the N-electron valence state perturbation theory (NEVPT2) were used to calculate energies and oscillator strengths for multiple excited electronic states. The number of active electrons and orbitals and the number of excited states included in state-averaged CASSCF were selected such that the accuracy of ab initio predictions could be improved systematically. The procedure introduced here for the calculation of multiple excited electronic states of TADF candidates can be used to accelerate the computational search for efficient TADF materials.

Seasonal dynamics and punctuated carbon sink reduction suggest photosynthetic capacity of boreal silver birch is reduced by the accumulation of hexose.

The 'assimilates inhibition hypothesis' posits that accumulation of nonstructural carbohydrates (NSCs) in leaves reduces leaf net photosynthetic rate, thus internally regulating photosynthesis. Experimental work provides equivocal support mostly under controlled conditions without identifying a particular NSC as involved in the regulation. We combined 3-yr in situ leaf gas exchange observations (natural dynamics) in the upper crown of mature Betula pendula simultaneously with measurements of concentrations of sucrose, hexoses (glucose and fructose), and starch, and similar measurements during several one-day shoot girdling (perturbation dynamics). Leaf water potential and water and nitrogen content were measured to account for their possible contribution to photosynthesis regulation. Leaf photosynthetic capacity (A/Ci) was temporally negatively correlated with NSC accumulation under both natural and perturbation states. For developed leaves, leaf hexose concentration explained A/Ci variation better than environmental variables (temperature history and daylength); the opposite was observed for developing leaves. The weaker correlations between NSCs and A/Ci in developing leaves may reflect their strong internal sink strength for carbohydrates. By contrast, the strong decline in photosynthetic capacity with NSCs accumulation in mature leaves, observed most clearly with hexose, and even more tightly with its constituents, provides support for the role of assimilates in regulating photosynthesis under natural conditions.