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Development of simple and effective synergistic therapy by combination of different therapeutic modalities within one single nanostructure is of great importance for cancer treatment. In this study, by integrating the anticancer drug DOX and plasmonic bimetal heterostructures into zeolitic imidazolate framework-8 (ZIF-8), a stimuli-responsive multifunctional nanoplatform, DOX-Pt-tipped Au@ZIF-8, has been successfully fabricated. Pt nanocrystals with catalase-like activity were selectively grown on the ends of the Au nanorods to form Pt-tipped Au NR heterostructures. Under single 1064 nm laser irradiation, compared with Au NRs and Pt-covered Au NRs, the Pt-tipped Au nanorods exhibit outstanding photothermal and photodynamic properties owing to more efficient plasmon-induced electron–hole separation. The heat generated by laser irradiation can enhance the catalytic activity of Pt and improve the O 2 level to relieve tumor hypoxia. Meanwhile, the strong absorption in the NIR-II region and high- Z elements (Au, Pt) of the DOX-Pt-tipped Au@ZIF-8 provide the possibility for photothermal (PT) and computed tomography (CT) imaging. Both in vitro and in vivo experimental results illustrated that the DOX-Pt-tipped Au@ZIF-8 exhibits remarkably synergistic plasmon-enhanced chemo-phototherapy (PTT/PDT) and successfully inhibited tumor growth. Taken together, this work contributes to designing a rational theranostic nanoplatform for PT/CT imaging-guided synergistic chemo-phototherapy under single laser activation.

Given the potential of peptide selenoesters for protein total synthesis and the paucity of methods for the synthesis of these sensitive peptide derivatives, we sought to explore the usefulness of the bis(2-selenylethyl)amido (SeEA) group, i.e. the selenium analog of the bis(2-sulfanylethyl)amido (SEA) group, for accelerating peptide bond formation. A chemoselective exchange process operating in water was devised for converting SEA peptides into the SeEA ones. Kinetic studies show that SeEA ligation, which relies on an initial N , Se -acyl shift process, proceeds significantly faster than SEA ligation. This property enabled the design of a kinetically controlled three peptide segment assembly process based on the sequential use of SeEA and SEA ligation reactions. The method was validated by the total synthesis of hepatocyte growth factor K1 (85 AA) and biotinylated NK1 (180 AA) domains.

Structure-based virtual screening is an important tool in early stage drug discovery that scores the interactions between a target protein and candidate ligands. As virtual libraries continue to grow (in excess of 10 8 molecules), so too do the resources necessary to conduct exhaustive virtual screening campaigns on these libraries. However, Bayesian optimization techniques, previously employed in other scientific discovery problems, can aid in their exploration: a surrogate structure–property relationship model trained on the predicted affinities of a subset of the library can be applied to the remaining library members, allowing the least promising compounds to be excluded from evaluation. In this study, we explore the application of these techniques to computational docking datasets and assess the impact of surrogate model architecture, acquisition function, and acquisition batch size on optimization performance. We observe significant reductions in computational costs; for example, using a directed-message passing neural network we can identify 94.8% or 89.3% of the top-50?000 ligands in a 100M member library after testing only 2.4% of candidate ligands using an upper confidence bound or greedy acquisition strategy, respectively. Such model-guided searches mitigate the increasing computational costs of screening increasingly large virtual libraries and can accelerate high-throughput virtual screening campaigns with applications beyond docking.

We have shown for the first time that taxadiene ( 3 ) can be epoxidised in a regio- and diastereoselective manner to provide taxadiene-4(5)-epoxide ( 12 ) as a single diastereoisomer, and that this epoxide can be rearranged to give taxa-4(20),11(12)-dien-5α-ol ( 4 ). Furthermore, the epoxide 12 rearranges under acidic conditions to give taxa-4(20),11(12)-dien-5α-ol ( 4 ), the known bridged ether OCT ( 5 ) and the new oxacyclotaxane (OCT2) 15 . Contrary to previous speculation, taxadiene-4(5)-epoxide ( 12 ) is susceptible to rearrangement when exposed to an iron III porphyrin, and these observations justify consideration of epoxide 12 as a chemically competent intermediate on the taxol biosynthetic pathway.

Metal thin films are indispensable for the processing of a number of modern devices that benefit from their electronic, magneto-electric and optical properties. Application trends progressively involve integration into functional devices which feature three-dimensional nanostructures with increasingly high aspect ratios. These conditions promote increased interest towards non-line-of-sight deposition processes such as Chemical Vapour Deposition ( CVD ) and Atomic Layer Deposition ( ALD ). The deposition of metals using CVD or ALD is, however, less developed than that of the oxide counterparts. Several persisting limitations are directly related to the deposition chemistry. In the present perspective, relevant deposition chemical approaches are discussed along with their corresponding characteristics. Challenging issues regarding the purity and the nucleation kinetics are addressed. Using the intrinsic reactivity of the metals themselves to catalyse their own growth is one of the promising approaches emphasised here. Based on our recent work, the potential of this approach is discussed with respect to the growth of reactive and noble transition metals, pure or as alloys, as thin films or as embedded nanoparticles in functional oxide matrix thin films.

Our computational and experimental studies show that the high order 1, n -zwitterionic intermediates ( n = 5, 7 and 9) of allenoate-PR 3 are real species. The cycloaddition reactions of these versatile intermediates with electrophilic-coupling partners provide novel and highly convergent synthetic approaches to medium- and large-ring compounds.

Fluorescence modulation for selective recovery of desired fluorescence signals has to date required careful fluorophore selection combined with repeated optical recovery from long-lived photoinduced dark states. Adapting an all-optical scheme, modulated stimulated emission depletion (STED) generalizes such modulation schemes by eliminating the need for dark state residence by directly optically depopulating the emissive state at any externally applied frequency. Using two overlapped Gaussian laser spots with the depletion beam being intensity-modulated, fluorescence modulation is readily achieved with a depletion ratio governed by the intensity of the depleting laser. Selective image recovery of otherwise unmodulatable fluorophore signals is directly achieved through this all-optical modulation, and common STED-degrading multiphoton-excited background is readily discriminated against. Both beads and dyes in solution, as well as fluorophores bound within fixed cells are readily imaged in this manner.

The energies of the 133?000 molecules in the GDB-9 database have been calculated at the G4MP2 level of theory and then were used to calculate their enthalpies of formation. This database contains organic molecules having nine or less atoms of carbon, nitrogen, oxygen, and fluorine, as well as hydrogen atoms. The accuracy of the G4MP2 energies was investigated on a subset of 459 of the molecules having experimental enthalpies of formation with small uncertainties. On this subset the G4MP2 enthalpies of formation have an accuracy of 0.79 kcal mol ?1 , which is similar to its accuracy previously reported for the smaller G3/05 test set. An error analysis of the theoretical enthalpies of formation of the 459 molecules is presented in terms of the size and type of the molecules. Three different density functionals (B3LYP, ωB97X-D, M06-2X) were also assessed on 459 molecules of accurate enthalpy data for comparison with the G4MP2 results. The G4MP2 energies for the 133 K molecules provide a database that can be used to calculate accurate reaction energies as well as to assess new or existing experimental enthalpies of formation. Several examples are given of types of reactions that can be predicted using the G4MP2 database of energies. The G4MP2 energies of the GDB-9 molecules will also be useful in future investigations of applications of machine learning to quantum chemical data.

Thermal control in low-emission windows is achieved by the application of glazings, which are simultaneously optically transparent in the visible and reflective in the near-infrared (IR). This phenomenon is characteristic of coatings with wide optical band gaps that have high enough charge carrier concentrations for the material to interact with electromagnetic radiation in the IR region. While conventional low-E coatings are composed of sandwiched structures of oxides and thin Ag films or of fluorinated SnO 2 coatings, ZnO-based glazing offers an environmentally stable and economical alternative with competitive optoelectronic properties. In this work, gallium-doped zinc oxide (GZO) coatings with properties for low-E coatings that exceed industrial standards ( T visible 82%; R 2500 nm 90%; λ (plasma) = 1290 nm; ρ = 4.7 × 10 ?4 Ω cm; R sh = 9.4 Ω·□ ?1 ) are deposited through a sustainable and environmentally friendly halogen-free deposition route from [Ga(acac) 3 ] and a pre-organized zinc oxide precursor [EtZnO i Pr] 4 ( 1 ) via single-pot aerosol-assisted chemical vapor deposition. GZO films are highly (002)-textured, smooth and compact without need of epitaxial growth. The method herein describes the synthesis of coatings with opto-electronic properties commonly achievable only through high-vacuum methods, and provides an alternative to the use of pyrophoric ZnEt 2 and halogenated SnO 2 coatings currently used in low-emission glazing and photovoltaic technology.

Increasing the efficiency of molecular artificial photosynthetic systems is mandatory for the construction of functional devices for solar fuel production. Decoupling the light-induced charge separation steps from the catalytic process is a promising strategy, which can be achieved thanks to the introduction of suitable electron relay units performing charge accumulation. We report here on a novel ruthenium tris-diimine complex able to temporarily store two electrons on a fused dipyridophenazine–pyridoquinolinone π-extended ligand upon visible-light irradiation in the presence of a sacrificial electron donor. Full characterization of this compound and of its singly and doubly reduced derivatives thanks to resonance Raman, EPR and (TD)DFT studies allowed us to localize the two electron-storage sites and to relate charge photoaccumulation with proton-coupled electron transfer processes.