Precise synthesis of unique polydopamine/mesoporous calcium phosphate hollow Janus nanoparticles for imaging-guided chemo-photothermal synergistic therapy.

Multifunctional polymer-inorganic Janus nanoparticles (JNPs) that simultaneously have therapeutic and imaging functions are highly desired in biomedical applications. Here, we fabricated spherical polydopamine/mesoporous calcium phosphate hollow JNPs (PDA/mCaP H-JNPs) via a novel and facile approach. The obtained PDA/mCaP H-JNPs were further selectively functionalized with indocyanine green (ICG) and methoxy-poly(ethylene glycol)thiol (PEG-SH) on PDA domains to achieve a superior photoacoustic (PA) imaging capability and stability, while the other mCaP sides with hollow cavities served as storage spaces and passages for the anti-cancer drug, doxorubicin (DOX). The resultant PEG-ICG-PDA/mCaP H-JNPs possess excellent biocompatibility, a competent drug loading capability, high photothermal conversion efficiency, strong near-infrared (NIR) absorbance, and pH/NIR dual-responsive properties, enabling the H-JNPs to be applied for PA imaging-guided synergistic cancer chemo-phototherapy in vitro and in vivo. Furthermore, the synthetic approach could be extended to prepare PDA/various mesoporous inorganic H-JNPs with spherical shapes for specific applications.

Tailored Synthesis of Octopus-type Janus Nanoparticles for Synergistic Actively-Targeted and Chemo-Photothermal Therapy.

A facile, reproducible, and scalable method was explored to construct uniform Au@poly(acrylic acid) (PAA) Janus nanoparticles (JNPs). The as-prepared JNPs were used as templates to preferentially grow a mesoporous silica (mSiO2 ) shell and Au branches separately modified with methoxy-poly(ethylene glycol)-thiol (PEG) to improve their stability, and lactobionic acid (LA) for tumor-specific targeting. The obtained octopus-type PEG-Au-PAA/mSiO2 -LA Janus NPs (PEG-OJNP-LA) possess pH and NIR dual-responsive release properties. Moreover, DOX-loaded PEG-OJNP-LA, upon 808 nm NIR light irradiation, exhibit obviously higher toxicity at the cellular and animal levels compared with chemotherapy or photothermal therapy alone, indicating the PEG-OJNP-LA could be utilized as a multifunctional nanoplatform for in vitro and in vivo actively-targeted and chemo-photothermal cancer therapy.

The facile synthesis of hollow Au nanoflowers for synergistic chemo-photothermal cancer therapy.

A novel, mild and facile synthetic route was first developed to fabricate hollow Au nanoflowers (designated as H-AuNFs) with drug loading capacity, superior photothermal conversion property and pH/NIR dual-responsive drug delivery performance.

DFT characterization on the mechanism of sulfoxidation with H2O2 catalyzed by tetranuclear peroxotungstates [XO4{WO(O2)2}4](n-) (X = Si(IV), P(V), S(VI), As(V), and Se(VI)).

A thorough theoretical analysis was carried out on the sulfoxidation with H2O2 catalyzed by a tetranuclear peroxotungstate [SiO4{WO(O2)2}4](4-). The active species is the [SiO4{WO(O2)2}4(H2O2)](4-) (SiW4(H2O2)) complex rather than [SiO4{WO(O2)2}4](4-) (SiW4). The catalytic cycle consists of three elementary processes: oxygen transfer, sulfoxide dissociation, and catalyst regeneration. The oxygen transfer occurs from the peroxo oxygen atom O1 of SiW4(H2O2) to the sulfur center of dimethyl sulfide with a moderate Gibbs activation energy (ΔG°(‡)) of 17.1 kcal mol(-1). By comparing potential energy surfaces and condensed Fukui functions (ƒ(+)), the electrophilicity of the outer peroxo atoms in SiW4(H2O2) determines which oxygen transfers to the dimethyl sulfide. Then, the sulfoxide dissociation proceeds with a small ΔG°(‡) value of 2.3 kcal mol(-1) by elongation of the peroxo O1-O4 distance and elimination of the product dimethylsulfoxide. Finally, the catalyst regeneration is found to occur via two successive proton transfers from H2O2 to the oxygen atoms of peroxotungstates with the ΔG°(‡) values of 15.9 and 15.3 kcal mol(-1), which has been firstly examined in the present study. All of these steps occur easily with moderate ΔG°(‡) values, but the oxygen transfer is the rate-determining step of this catalytic reaction. In addition, the catalytic activity of peroxotungstates can be effectively tuned by changing the heteroatom X of [XO4{WO(O2)2}4(H2O2)](n-) in the order: Se(VI) ≈ S(VI) > As(V) ≈ P(V) > Si(IV).

Assembly of Fe-substituted Dawson-type nanoscale selenotungstate clusters with photocatalytic H2 evolution activity.

Two Fe-substituted Dawson-type nanoscale selenotungstate clusters, {Fe6Se6W34} and {Fe10Se8W62} involving {α-Se2W14} and {γ-Se2W14} building blocks, have been isolated, which exhibit photocatalytic H2 evolution activity. Their electrochemical behaviours and magnetic properties were also investigated.

Reversible redox-switchable second-order optical nonlinearity in polyoxometalate: a quantum chemical study of [PW11O39(ReN)]n- (n = 3-7).

In this paper, the relationship between the reversible redox properties and the second-order nonlinear optical (NLO) responses for the title series of complexes has been systematically investigated by using the time-dependent density functional theory (TDDFT) method combined with the sum-over-states (SOS) formalism. The results reveal that the successive reduction processes of five PW11ReN redox states should be PW11ReVII (1) --> PW11ReVI (2) --> PW11ReV (3) --> PW11ReV1e ( 4) --> PW 11ReV2e (5). Furthermore, their electrochemical properties have been reproduced successfully. It is noteworthy that the second-order NLO behaviors can be switched by reversible redox for the present studied complexes. Full oxidation constitutes a convenient way to switch off the second-order polarizability (system 1). The incorporation of extra electrons causes significant enhancement in the second-order NLO activity, especially for the third reduced state (system 4), whose static second-order polarizability (betavec) is about 144 times larger than that of fully oxidized 1. The characteristic of the charge-transfer transition corresponding to the dominant contributions to the betavec values indicates that metal-centered redox processes influence the intramolecular donor or acceptor character. Therefore, these kinds of complexes with the facile and reversible redox states could become excellent switchable NLO materials.