Search

We derive an analytic expression of the non-equilibrium Fermi's golden rule (NE-FGR) expression for a Holstein–Tavis–Cumming Hamiltonian, a universal model for many molecules collectively coupled to the optical cavity. These NE-FGR expressions capture the full-time-dependent behavior of the rate constant for transitions from polariton states to dark states. The rate is shown to be reduced to the well-known frequency domain-based equilibrium Fermi's golden rule (E-FGR) expression in the equilibrium and collective limit and is shown to retain the same scaling with the number of sites in non-equilibrium and non-collective cases. We use these NE-FGR to perform population dynamics with a time-non-local and time-local quantum master equation and obtain accurate population dynamics from the initially occupied upper or lower polariton states. Furthermore, NE-FGR significantly improves the accuracy of the population dynamics when starting from the lower polariton compared to the E-FGR theory, highlighting the importance of the non-Markovian behavior and the short-time transient behavior in the transition rate constant. [ABSTRACT FROM AUTHOR]

We extend our recently proposed theoretical framework for estimating cavity-modified equilibrium Fermi's golden rule (FGR) rate constants beyond the single cavity mode case to cases where the molecular system is coupled to multiple cavity modes. We show that the cumulative effect of simultaneous coupling to multiple modes can enhance FGR rate constants by orders of magnitude relative to the single mode case. We also present an analysis of the conditions necessary for maximizing this effect in the Marcus limit of FGR-based rate theory. [ABSTRACT FROM AUTHOR]

A new method of spatially controlled gene regulation in 3D-cultured human embryonic stem cells is developed using hollow gold nanoshells (HGNs) and near-infrared (NIR) light. Targeted cell(s) are discriminated from neighboring cell(s) by focusing NIR light emitted from a two-photon microscope. Irradiation of cells that have internalized HGNs releases surface attached siRNAs and leads to concomitant gene downregulation.

Quantum master equations (QMEs) provide a general framework for describing electronic dynamics within a complex molecular system. Off-diagonal QMEs (OD-QMEs) correspond to a family of QMEs that describe the electronic dynamics in the interaction picture based on treating the off-diagonal coupling terms between electronic states as a small perturbation within the framework of second-order perturbation theory. The fact that OD-QMEs are given in terms of the interaction picture makes it non-trivial to obtain Schrödinger picture electronic coherences from them. A key experimental quantity that relies on the ability to obtain accurate Schrödinger picture electronic coherences is the absorption spectrum. In this paper, we propose using a recently introduced procedure for extracting Schrödinger picture electronic coherences from interaction picture inputs to calculate electronic absorption spectra from the electronic dynamics generated by OD-QMEs. The accuracy of the absorption spectra obtained this way is studied in the context of a biexciton benchmark model, by comparing spectra calculated based on time-local and time-nonlocal OD-QMEs to spectra calculated based on a Redfield-type QME and the non-perturbative and quantum-mechanically exact hierarchical equations of motion method. [ABSTRACT FROM AUTHOR]

Quantum master equations provide a general framework for describing the dynamics of electronic observables within a complex molecular system. One particular family of such equations is based on treating the off-diagonal coupling terms between electronic states as a small perturbation within the framework of second-order perturbation theory. In this paper, we show how different choices of projection operators, as well as whether one starts out with the time-convolution or the time-convolutionless forms of the generalized quantum master equation, give rise to four different types of such off-diagonal quantum master equations (OD-QMEs), namely, time-convolution and time-convolutionless versions of a Pauli-type OD-QME for only the electronic populations and an OD-QME for the full electronic density matrix (including both electronic populations and coherences). The fact that those OD-QMEs are given in terms of the interaction picture makes it non-trivial to obtain Schrödinger picture electronic coherences from them. To address this, we also extend a procedure for extracting Schrödinger picture electronic coherences from interaction picture populations recently introduced by Trushechkin in the context of time-convolutionless Pauli-type OD-QME to the other three types of OD-QMEs. The performance of the aforementioned four types of OD-QMEs is explored in the context of the Garg–Onuchic–Ambegaokar benchmark model for charge transfer in the condensed phase across a relatively wide parameter range. The results show that time-convolution OD-QMEs can be significantly more accurate than their time-convolutionless counterparts, particularly in the case of Pauli-type OD-QMEs, and that rather accurate Schrödinger picture coherences can be obtained from interaction picture electronic inputs. [ABSTRACT FROM AUTHOR]

Primary open-angle glaucoma (POAG) is the most common form of glaucoma and the leading cause of irreversible vision loss and blindness worldwide. Intraocular pressure (IOP) is the only modifiable risk factor, and prompt treatment to lower IOP can effectively slow the rate of vision loss due to glaucoma. Trabecular meshwork (TM) cells can maintain IOP homeostasis by correcting and adjusting the resistance to aqueous humor outflow in response to sustained pressure changes. TM cells' function is reduced, and membrane ion channels are impaired in POAG. The dysfunction of Large conductance Ca 2+ -activated K + (BKCa) plays a central role in the pathogenesis of POAG. In this work, we targeted MXene nanoparticles (MXene-RGD) with piezoelectric response to TM cells in a 3D model of glaucoma in vitro as well as in the rabbit Transient Ocular Hypertension (OHT) Model in vivo . MXene-RGD gives the TM electromechanical transfer properties, while the self-enhancing and self-generated electricity properties of the TM are determined by the aqueous humor flow rate and the size of the deformation of the TM. MXene-RGD is nontoxic, as illustrated by a cell toxicity study and histological examination. In a 3D in vitro model of high-pressure glaucoma, whole-cell patch-clamp confirmed that piezoelectric stimulation turns on BKCa, which reduces the volume of the cell. MXene-RGD was injected into the anterior chamber with minimal trauma, i.e. , anterior chamber injection, and specifically targeted to TM cells. The OHT model in vivo confirmed the potential IOP-lowering ability of MXene-RGD. We evaluated the ion channels involved in the reduction of IOP by MXene-RGD by pre-treatment with a BKCa channel blocker (iberiotoxin, IbTX) and a voltage-gated Ca 2+ channel blocker (nifedipine). Quantitative qPCR analysis showed that MXene-RGD inhibited the upregulation of mRNA expression levels of the myofibroblast marker α-smooth muscle actin (α-SMA) and the inflammatory response marker interleukin-6 (IL-6) induced by IOP. Histology confirmed that MXene-RGD attenuated IOP-induced proliferation and collagen production in the TM. Taken together, we present for the first time a minimally invasive surgical approach for targeting TM cells for POAG by utilizing piezoresponse nanomaterials to target BKCa to repair or awaken the ability of TM cells to regulate IOP homeostasis on their own.

In the context of diabetes, endothelial cells frequently exhibit compromised intercellular junctions and accelerated cellular senescence simultaneously. The precise mechanisms underlying these issues and the identification of effective treatments remain largely undefined. Our findings reveal that human umbilical vein endothelial cells (HUVECs) can counteract senescence and uphold the integrity of intercellular junctions under mildly to moderately elevated glucose levels (10 mM and 15 mM) via two primary mechanisms: i) The acetylation of NRF2 at lysine residues K56, K68, and K52 prevents its ubiquitination, enhancing the transcription of antioxidant genes GST, SOD1, and GPX1. This activity diminishes cytoplasmic oxidative stress, thereby mitigating endothelial cell senescence. ii) The interaction between the Neh2 domain of NRF2 and the PAS-B domain of HIF-2α within the nucleus curtails the attachment of HIF-2α to the NOX4/p22phox promoter. This action lessens oxidative stress near the cell membrane, maintaining intercellular junctions by safeguarding the disulfide bonds in occludin and E-cadherin from disruption. However, these protective strategies prove insufficient under severe hyperglycemic conditions (25 mM). Further investigation has identified Oltipraz, an activator of NRF2, as also promoting the degradation of HIF-2α. Through its simultaneous modulation of NRF2 and HIF-2α, Oltipraz significantly reduces cellular senescence and prevents the deterioration of intercellular junctions in HUVECs subjected to high glucose concentrations (25 mM). Our research positions Oltipraz as a promising therapeutic candidate for mitigating diabetes-induced vascular endothelial damage, potentially offering benefits against diabetes-related atherosclerosis and valvular calcification., Competing Interests: Competing Interests: The authors have declared that no competing interest exists., (© The author(s).)