Janus Gold Nanostars–Mesoporous Silica Nanoparticles for NIR-Light-Triggered Drug Delivery

Janus gold nanostar–mesoporous silica nanoparticle ( AuNSt–MSNP ) nanodevices able to release an entrapped payload upon irradiation with near infrared (NIR) light were prepared and characterized. The AuNSt surface was functionalized with a thiolated photolabile molecule ( 5 ), whereas the mesoporous silica face was loaded with a model drug (doxorubicin) and capped with proton-responsive benzimidazole-β-cyclodextrin supramolecular gatekeepers ( N 1 ). Upon irradiation with NIR-light, the photolabile compound 5 photodissociated, resulting in the formation of succinic acid, which induced the opening of the gatekeeper and cargo delivery. In the overall mechanism, the gold surface acts as a photochemical transducer capable of transforming the NIR-light input into a chemical messenger (succinic acid) that opens the supramolecular nanovalve. The prepared hybrid nanoparticles were non-cytotoxic to HeLa cells, until they were irradiated with a NIR laser, which led to intracellular doxorubicin release and hyperthermia. This induced a remarkable reduction in HeLa cells viability.     

Inner-Sphere Oxygen Activation Promoting Outer-Sphere Nucleophilic Attack on Olefins

Alkoxylation and hydroxylation reactions of 1,5-cyclooctadiene (cod) in an iridium complex with alcohols and water promoted by the reduction of oxygen to hydrogen peroxide are described. The exo configuration of the OH/OR groups in the products agrees with nucleophilic attack at the external face of the olefin as the key step. The reactions also require the presence of a coordinating protic acid (such as picolinic acid (Hpic)) and involve the participation of a cationic diolefin iridium(III) complex, [Ir(cod)(pic)₂]⁺, which has been isolated. Independently, this cation is also involved in easy alkoxy group exchange reactions, which are very unusual for organic ethers. DFT studies on the mechanism of olefin alkoxylation mediated by oxygen show a low-energy proton-coupled electron-transfer step connecting a superoxide–iridium(II) complex with hydroperoxide–iridium(III) intermediates, rather than peroxide complexes. Accordingly, a more complex reaction, with up to four different products, occurred upon reacting the diolefin–peroxide iridium(III) complex with Hpic. Moreover, such hydroperoxide intermediates are the origin of the regio- and stereoselectivity of the hydroxylation/alkoxylation reactions. If this protocol is applied to the diolefin–rhodium(I) complex [Rh(pic)(cod)], free alkyl ethers ORC₈H₁₁ (R=Me, Et) resulted, and the reaction is enantioselective if a chiral amino acid, such as l -proline, is used instead of Hpic.     

Mono-Aryl/Alkylthio-Substituted (Hetero)acenes of Exceptional Thermal and Photochemical Stability by the Thio-Friedel–Crafts/Bradsher Cyclization Reaction

The highly substituted mono-aryl/alkylthio-(hetero)acenes prepared in this study have been found to be thermally more stable (T_decomp.=331–354 °C) than the known di-aryl/alkylthio-substituted acenes by an average of 25 °C. They are also much more photostable at 254 and 365 nm (in both argon and air) than the parent anthracene and other reported anthracenes. The most photostable aryl/alkylthio-anthracenes at 254 nm were found to be 60–70 (in air) and 130 (in argon) times more stable in solution than the unsubstituted anthracene, and much more stable than known EDG/EWG-substituted anthracenes (EDG=electron-donating group, EWG=electron-withdrawing group) with an extended aromatic core. Furthermore, the acenes showed significantly higher photostability at 365 nm in both air and argon. The anthracenes were obtained by the novel thio-Friedel–Crafts/Bradsher cyclization reaction of hitherto unknown [o-(1,3-dithian-2-yl)aryl](aryl)methyl thioethers. The developed approach provides a general access to mono-aryl/alkylthio-substituted (hetero)acene frameworks containing at least three fused (hetero)aromatic rings. The characteristic feature of this approach, which leads to highly substituted acenes, is that the substituents, unlike in other methods, may be introduced at an early stage of the synthesis. DFT and TD-DFT calculations confirmed the stabilizing role of the aryl/alkylthio substituent in the mono-aryl/alkylthio-substituted anthracenes, which are the most stable anthracenes prepared to date. Their high photostability is mainly due to the quenching of singlet oxygen by the acene and the quenching of the acene S₁ state by molecular oxygen.     

Synthesis of Pure Silica MWW Zeolite in Fluoride Medium by Using an Imidazolium-Based Long Dication

As the spacer length in 1,2-dimethylimidazolium-based dications increases beyond a specific point (six methylene units), they fail in structure-directing towards STW zeolites in any synthetic conditions. These dications can instead produce, under fluoride concentrated conditions, either *BEA [in the case of the eight-methylene-unit structure-directing agent (SDA)] or MWW (ten methylene units) zeolites. For any length of the dication, the default zeolite (MTW) is a relatively dense zeolite containing a unidimensional channel, whereas the zeolite demanding most specificity (STW, *BEA or MWW) is more porous, affording a larger concentration of the dication to be occluded. This work provides the first reported fluoride synthesis of pure silica MWW zeolites. Charge balance of the organic dications in this zeolite was achieved by combining “structural” silanolates, regular “connectivity defects” and occluded fluoride. Molecular mechanics calculations showed a perfect fit of the decamethylenebis(dimethylimidazolium) dication in the sinusoidal intralayer pore system of MWW. The calculations showed also that the dication is able to stabilize the interlayer space without disturbing the hydrogen-bonding system that holds the layers together in the as-made material. The ¹⁹F magic-angle spinning (MAS) NMR presented two distinct resonances at −71 and −83 ppm, which, on the basis of DFT calculations, we tentatively assigned to fluoride occluded in [4⁶6²] and [4¹5²6²] cages of the MWW structure, respectively. The same DFT study determines a different chemical shift of one methyl ¹³C nuclear magnetic resonance according to the imidazolium ring residing in the sinusoidal channels or in the large cup cavities, thus explaining an experimentally observed splitting of that resonance.     

Recent Progress on Manganese-Based Nanostructures as Responsive MRI Contrast Agents

Manganese-based nanostructured contrast agents (CAs) entered the field of medical diagnosis through magnetic resonance imaging (MRI) some years ago. Although some of these Mn-based CAs behave as classic T₁ contrast enhancers in the same way as clinical Gd-based molecules do, a new type of Mn nanomaterials have been developed to improve MRI sensitivity and potentially gather new functional information from tissues by using traditional T₁ contrast enhanced MRI. These nanomaterials have been designed to respond to biological environments, mainly to pH and redox potential variations. In many cases, the differences in signal generation in these responsive Mn-based nanostructures come from intrinsic changes in the magnetic properties of Mn cations depending on their oxidation state. In other cases, no changes in the nature of Mn take place, but rather the nanomaterial as a whole responds to the change in the environment through different mechanisms, including changes in integrity and hydration state. This review focusses on the chemistry and MR performance of these responsive Mn-based nanomaterials.     

Anomeric effect in pyranose-ring derivatives containing carbon,silicon, and germanium as anomeric centers: an ab initio systematic study

Structural Chemistry - We have performed a systematic conformational analysis focused on the evaluation of the anomeric effect (AE) in a series of pyranose derivatives containing carbon, silicon,...     

The impact of time on the heat resistance of self-compacting high-performance concrete incorporated with recycled martials

The influence of time on the mechanical behavior of concrete after exposure to elevated temperatures has been studied. Twenty-one self-compacting high-performance concrete mixtures with different incorporation amounts of coarse recycled concrete aggregate (RCA) and three unprocessed waste powder materials have been tested at age of 270 days for residual compressive and flexural strength after exposure to fire. The results have been compared to the results for the same concrete, which have been studied at age of 90 days. A new parameter has been introduced for comparing the responses of concrete to elevated temperatures at different ages; this parameter was the “heat resistance” which expresses the total area under the curve of the relative residual strength (compressive or flexural) after exposing to six temperature degrees (20, 150, 300, 500, 600, and 800 °C). The results showed that the age of concrete has an influence on the response of concrete to elevated temperatures. The heat resistance of compressive strength enhanced with age but the concrete behaved with a tendency different to that at the age of 90 days. The heat resistance of flexural strength has not been affected or slightly decreased but not with more than 10% to that at the age of 90 days. The used waste powder materials were unprocessed waste fly ash, waste cellular concrete powder and waste perlite powder; they proved that using any of them up to 15% as a replacement for cement with 0% or 25% of RCA enhanced the concrete resistance for the fire with time. The main two reasons for changing of residual strength with the time were the changing of water content and the proceeding of hydration of the binder. In general, long ages testing properties of concrete simulate the real behavior of concrete structures accurately.

     

Thermal behaviour of materials in interrupted phase change

Journal of Thermal Analysis and Calorimetry - The most critical part and barrier of phase change material (PCM) applications are the accuracy of simulations and the control of the process. The...     

Crossing VIMP and EIS for studying heterogeneous sets of copper/bronze coins

Journal of Solid State Electrochemistry - Electrochemical impedance spectroscopy (EIS) and voltammetry of immobilized particles (VIMP) measurements using air-saturated mineral water and...     

Flow of Emulsions Stabilized by Polymers Through Packed Bed

Transport in Porous Media - In this study, we present the results of measurements of pressure drops during the flow of emulsions stabilized by carboxymethylcellulose sodium salt (NaCMC), xanthan...