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Due to the difficulty of accurately characterizing properties such as the molecular weight (Mn) and grafting density (σ) of gradient brushes (GBs), these properties are traditionally assumed to be uniform in space to simplify analysis. Applying a stochastic reaction model (SRM) developed for heterogeneous polymerizations, we explored surface-initiated polymerizations (SIPs) with initiator gradients in lattice Monte Carlo simulations to examine this assumption. An initial exploration of SIPs with 'homogeneously' distributed initiators revealed that increasing σ slows down the polymerization process, resulting in polymers with lower molecular weight and larger dispersity (Đ) for a given reaction time. In SIPs with an initiator gradient, we observed that the properties of the polymers are position-dependent, with lower Mn and larger Đ in regions of higher σ, indicating the non-uniform properties of polymers in GBs. The results reveal a significant deviation in the scaling behavior of brush height with σ compared to experimental data and theoretical predictions, and this deviation is attributed to the non-uniform Mn and Đ. [ABSTRACT FROM AUTHOR]

Hypoxia is a critical factor for restricting photodynamic therapy (PDT) of tumor, and it becomes increasingly severe with increasing tissue depth. Thus, the relief of deep tumor hypoxia is extremely important to improve the PDT efficacy. Herein, tumor microenvironment (TME)‐responsive size‐switchable hyaluronic acid‐hybridized Ru nanoaggregates (HA@Ru NAs) were developed via screening reaction temperature to alleviate deep tumor hypoxia for improving the tumor‐specific PDT by the artful integration multiple bioactivated chemical reactions in situ and receptor‐mediated targeting (RMT). In this nanosystem, Ru NPs not only enabled HA@Ru NAs to have near infrared (NIR)‐mediated photothermal/photodynamic functions, but also could catalyze endogenous H2O2 to produce O2in situ. More importantly, hyaluronidase (HAase) overexpressed in the TME could trigger disassembly of HA@Ru NAs via the hydrolysis of HA, offering the smart size switch capability from 60 to 15 nm for enhancing tumor penetration. Moreover, the RMT characteristics of HA ensured that HA@Ru NAs could specially enter CD44‐overexpressed tumor cells, enhancing tumor‐specific precision of phototherapy. Taken together these distinguishing characteristics, smart HA@Ru NAs successfully realized the relief of deep tumor hypoxia to improve the tumor‐specific PDT. [ABSTRACT FROM AUTHOR]

The stochastic reaction model (SRM) treats polymerization as a pure probability‐based issue, which is widely applied to simulate various polymerization processes. However, in many studies, active centers were assumed to react with the same probability, which cannot reflect the heterogeneous reaction microenvironment in heterogeneous polymerizations. Recently, we have proposed a simple SRM, in which the reaction probability of an active center is directly determined by the local reaction microenvironment. In this paper, we compared this simple SRM with other SRMs by examining living polymerizations with randomly dispersed and spatially localized initiators. The results confirmed that the reaction microenvironment plays an important role in heterogeneous polymerizations. This simple SRM provides a good choice to simulate various polymerizations. [ABSTRACT FROM AUTHOR]

In order to study the dynamics of colloidal suspensions with viscoelastic solvents, a simple mesoscopic model of the solvent is required. We propose to extend the multiparticle collision dynamics (MPC) technique-a particle-based simulation method, which has been successfully applied to study the hydrodynamic behavior of many complex fluids with Newtonian solvent-to shear-thinning viscoelastic solvents. Here, the normal MPC particles are replaced by dumbbells with finite-extensible nonlinear elastic (FENE) springs. We have studied the properties of FENE-dumbbell fluids under simple shear flow with shear rate γ. The stress tensor is calculated, and the viscosity η and the first normal-stress coefficient Ψ1 are obtained. Shear-thinning behavior is found for reduced shear rates Γ=γτ>1, where τ is a characteristic dumbbell relaxation time. Here, both η and Ψ1 display power-law behavior in the shear-thinning regime. Thus, the FENE-dumbbell fluid with MPC collisions provides a good description of viscoelastic fluids. As a first application, we study the flow behavior of a colloid in a shear-thinning viscoelastic fluid in two dimensions. A slowing down of the colloid rotation in a viscoelastic fluid compared to a Newtonian fluid is obtained, in agreement with recent numerical calculations and experimental results. [ABSTRACT FROM AUTHOR]

This paper has extended nonequilibrium Monte Carlo (MC) approach to simulate oscillatory shear flow in a lattice block copolymer system. Phase transition and associated rheological behaviors of multiple self-avoiding chains have been investigated. Stress tensor has been obtained based upon sampled configuration distribution functions. At low temperatures, micellar structures have been observed and the underlying frequency-dependent rheological properties exhibit different initial slopes. The simulation outputs are consistent with the experimental observations in literature. Chain deformation during oscillatory shear flow has also been revealed. Although MC simulation cannot account for hydrodynamic interaction, the highlight of our simulation approach is that it can, at small computing cost, investigate polymer chains simultaneously at different spatial scales, i.e., macroscopic rheological behaviors, mesoscopic self-assembled structures, and microscopic chain configurations. [ABSTRACT FROM AUTHOR]

Sulfur dioxide (SO2) derivatives play critical roles in various biological processes. Therefore, effective methods for monitoring SO2 are of vital importance in bisulfite/sulfite biology. In this study, a two-photon (TP) imaging probe (CQ-SO2) for detecting SO2 derivatives was designed and constructed, based on the chromenoquinoline (CQ) fluorophore and a β-chlorovinyl aldehyde sensing moiety. The TP properties of the CQ derivatives were revealed for the first time in this study. This study enriched the biological application range of CQ derivatives and also provided a new choice for the development of TP dyes. In particular, the CQ-SO2 probe exhibited a fast response time (about 5 s), low detection limit (16 nM) and ultrahigh specificity towards SO2 derivatives. Furthermore, the probe was successfully applied to the highly specific TP bioimaging of SO2 derivatives in living cells and zebrafish. [ABSTRACT FROM AUTHOR]

Abstract: Indocyanine green (ICG) is an effective light absorber for laser‐mediated photodynamic therapy. However, applications of ICG are limited due to its rapid degradation and poor photostability in water. Herein, we report the development of a multifunctional nanoplatform by coating ICG on the surface of single‐walled carbon nanohorns (SWNHs) through π–π stacking, obtaining SWNH‐ICGs with high solubility and stability under physiological conditions. The SWNH‐ICGs could be used as a single nanoplatform to simultaneously produce satisfactory hyperthermia and reactive oxygen species under near‐infrared (NIR) laser irradiation. In addition, the SWNH‐ICGs not only improved the photostability of ICG in different media, but also protected it from light degradation. The SWNH‐ICGs exhibited highly efficient thermal/photoacoustic (PA) imaging‐guided photothermal therapy (PTT) and photodynamic therapy (PDT) effects, even under low‐power laser irradiation (0.3 W cm−2) in vitro. Combined PTT and PDT effectively killed triple‐negative breast cancer 4T1 cells, demonstrating a markedly improved and synergistic therapeutic effect compared to PTT or PDT alone. Furthermore, significant tumor growth inhibition as well as tumor cell death were observed following PTT/PDT at 808 nm laser irradiation, confirming the synergistic effects of SWNH‐ICGs over free ICG in vivo. This facile and simple methodology for thermal/PA imaging‐guided PTT/PDT suggests that SWNH‐ICGs may serve as an effective nanoplatform for cancer therapy. [ABSTRACT FROM AUTHOR]

Treatment in combination with real-time monitoring of dynamic organelle changes is of great significance for evaluating therapeutic efficacy. However, it remains highly challenging to realize such specific treatment and monitoring in organelles. Herein, we developed one kind of red emissive two-photon carbon dots (TP-CDs) via an N doping strategy for nucleolus-targeted treatment combined with real-time monitoring of dynamic changes in the nucleolus. In the TP-CD system, N doping endows TP-CDs with intrinsic two-photon excitation, red emission at 605 nm, and singlet oxygen (1O 2) production under 638 nm laser irradiation. More importantly, N heterocycles induced by doping offers significant affinity for TP-CDs toward RNA to realize specific self-targeting toward nucleolus and fluorescence variation during the photodynamic therapy (PDT) via the cleaving of RNA chain by 1O 2 to dissociate TP-CDs@RNA complex. By combining 1O 2 production, fluorescent variation during the PDT process, long-wavelength excitation and emission characteristics, as well as specific self-targetability of nucleolus, TP-CDs can be considered as a kind of "smart" CDs to realize treatment in combination of real-time dynamic changes in nucleolus for the first time. [Display omitted] [ABSTRACT FROM AUTHOR]

The tumor immunosuppressive microenvironment (TIME) and uncontrollable release of antigens can lower the efficacy of nanovaccine-based immunotherapy (NBI). Therefore, it is necessary to develop a new strategy for TIME reshaping and controllable release of antigens to improve the NBI efficacy. Herein, an acidity-responsive Schiff base-conjugated polyphenol-coordinated nanovaccine was constructed for the first time to realize bidirectional TIME reshaping and controllable release of antigens for activating T cells. In particular, an acidity-responsive tannic acid-ovalbumin (TA-OVA) nanoconjugate was prepared via a Schiff base reaction. Fe III was coordinated with TA-OVA to produce a Fe III -TA-OVA nanosystem, and 1-methyltryptophan (1-MT) as an indoleamine 2,3-dioxygenase inhibitor was loaded to form a polyphenol-coordinated nanovaccine. The coordination between Fe III and TA could cause photothermal ablation of primary tumors, and the acidity-triggered Schiff base dissociation of TA-OVA could controllably release OVA to realize lysosome escape, initiating the body's immune response. More importantly, oxidative stress generated by a tumor-specific Fenton reaction of Fe ions could promote the polarization of tumor-associated macrophages from the M2 to M1 phenotype, resulting in the upregulation of cytotoxic T cells and helper T cells. Meanwhile, 1-MT could downregulate immunosuppressive regulatory T cells. Overall, such skillful combination of bidirectional TIME reshaping and controllable antigen release into one coordination nanosystem could effectively enhance the NBI efficacy of tumors.

Hypoxia is a critical factor for restricting photodynamic therapy (PDT) of tumor, and it becomes increasingly severe with increasing tissue depth. Thus, the relief of deep tumor hypoxia is extremely important to improve the PDT efficacy. Herein, tumor microenvironment (TME)-responsive size-switchable hyaluronic acid-hybridized Ru nanoaggregates (HA@Ru NAs) were developed via screening reaction temperature to alleviate deep tumor hypoxia for improving the tumor-specific PDT by the artful integration multiple bioactivated chemical reactions in situ and receptor-mediated targeting (RMT). In this nanosystem, Ru NPs not only enabled HA@Ru NAs to have near infrared (NIR)-mediated photothermal/photodynamic functions, but also could catalyze endogenous H 2 O 2 to produce O 2 in situ. More importantly, hyaluronidase (HAase) overexpressed in the TME could trigger disassembly of HA@Ru NAs via the hydrolysis of HA, offering the smart size switch capability from 60 to 15 nm for enhancing tumor penetration. Moreover, the RMT characteristics of HA ensured that HA@Ru NAs could specially enter CD44-overexpressed tumor cells, enhancing tumor-specific precision of phototherapy. Taken together these distinguishing characteristics, smart HA@Ru NAs successfully realized the relief of deep tumor hypoxia to improve the tumor-specific PDT., (© 2024 Wiley‐VCH GmbH.)

Indocyanine green (ICG) is an effective light absorber for laser-mediated photodynamic therapy. However, applications of ICG are limited due to its rapid degradation and poor photostability in water. Herein, we report the development of a multifunctional nanoplatform by coating ICG on the surface of single-walled carbon nanohorns (SWNHs) through π-π stacking, obtaining SWNH-ICGs with high solubility and stability under physiological conditions. The SWNH-ICGs could be used as a single nanoplatform to simultaneously produce satisfactory hyperthermia and reactive oxygen species under near-infrared (NIR) laser irradiation. In addition, the SWNH-ICGs not only improved the photostability of ICG in different media, but also protected it from light degradation. The SWNH-ICGs exhibited highly efficient thermal/photoacoustic (PA) imaging-guided photothermal therapy (PTT) and photodynamic therapy (PDT) effects, even under low-power laser irradiation (0.3 W cm -2 ) in vitro. Combined PTT and PDT effectively killed triple-negative breast cancer 4T1 cells, demonstrating a markedly improved and synergistic therapeutic effect compared to PTT or PDT alone. Furthermore, significant tumor growth inhibition as well as tumor cell death were observed following PTT/PDT at 808 nm laser irradiation, confirming the synergistic effects of SWNH-ICGs over free ICG in vivo. This facile and simple methodology for thermal/PA imaging-guided PTT/PDT suggests that SWNH-ICGs may serve as an effective nanoplatform for cancer therapy., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The spontaneous formation of vesicles from amphiphiles with dispersed molecular weight (MW) as well as with mono-MW has been studied by a lattice Monte Carlo simulation. Both pure and mixed amphiphiles were self-assembled into vesicles under appropriate conditions. When mixed amphiphiles were examined, the amphiphiles with longer hydrophilic blocks preferred to segregate into the outer monolayer of the resultant vesicles, which is consistent with the experimental observations in recent literature. The kinetic study reveals that the increase of vesicle size is mainly caused by the mechanism of vesicle fusion at the early stage, and the evaporation-condensation mechanism cannot be neglected at the late stage. The fusion of vesicles is accompanied by translocation of chains from the outer monolayer to the inner monolayer. For mixed amphiphiles, the degree of segregation exhibits a size dependence of the vesicle. Compared to the chains with shorter hydrophilic blocks, those with longer hydrophilic blocks exhibit stronger trends to translocate from the outer monolayer to the inner one in vesicle self-adjustment, which leads to the quasi-equilibrium asymmetric distribution of the hydrophilic blocks in the post-fused vesicles.

The rheological behaviors of polymer brush under oscillatory shear flow were investigated by nonequilibrium Monte Carlo simulation. The grafted chain under oscillatory shear flow exhibited a waggling behavior like a flower, and the segments were found to have different oscillatory phases along the chain contour. Stress tensor was further obtained based on the statistics of sampled configuration distribution functions. The simulation reproduced the abrupt increase of the first normal stress difference N(1) with the flow velocity over a critical value, as observed in the experiment of Klein et al. [Nature (London) 352, 143 (1991)]. However, our simulation did not reproduce the brush thickening with shear velocity increased, which was suggested to be responsible for the abrupt increase of N(1) in the above-mentioned paper. This simulation demonstrates that the increase of normal stress might be an inherent behavior of polymer brush due to chain deformation under flow.