Theranostic Iron@Gold Core–Shell Nanoparticles for Simultaneous Hyperthermia‐Chemotherapy upon Photo‐Stimulation

The challenges of nanoparticles, such as size‐dependent toxicity, nonbiocompatibility, or inability to undergo functionalization for drug conjugation, limit their biomedical application in more than one domain. Oval‐shaped iron@gold core–shell (oFe@Au) magnetic nanoparticles are engineered and their applications in magnetic resonance imaging (MRI), optical coherence tomography (OCT), and controlled drug release, are explored via photo stimulation‐generated hyperthermia. The oFe@Au nanoparticles have a size of 42.57 ± 5.99 nm and consist of 10.76 and 89.24 atomic % of Fe and Au, respectively. Upon photo‐stimulation for 10 and 15 minutes, the levels of cancer cell death induced by methotrexate‐conjugated oFe@Au nanoparticles are sixfold and fourfold higher, respectively, than oFe@Au nanoparticles alone. MRI and OCT confirm the application of these nanoparticles as a contrast agent. Finally, results of in vivo experiments reveal that the temperature is elevated by 13.2 °C, when oFe@Au nanoparticles are irradiated with a 167 mW cm^?2 808 nm laser, which results in a significant reduction in tumor volume and scab formation after 7 days, followed by complete disappearance after 14 days. The ability of these nanoparticles to generate heat upon photo‐stimulation also opens new doors for studying hyperthermia‐mediated controlled drug release for cancer therapy. Applications include biomedical engineering, cancer therapy, and theranostics fields.     

Extended Birkhoff’s theorem in <Emphasis Type="Italic">f</Emphasis>(<Emphasis Type="Italic">T</Emphasis>) gravity

f(T) theory, a generally modified teleparallel gravity, has been proposed as an alternative gravity model to account for the dark energy phenomena. Following our previous work [Xin-he Meng and Ying-bin Wang, Eur. Phys. J. (2011), ], we prove that Birkhoff’s theorem holds in a more general context, specifically with the off diagonal tetrad case, in this communication letter. Then, we discuss, respectively, the results of the external vacuum and internal gravitational field in the f(T) gravity framework, as well as the extended meaning of this theorem. We also investigate the validity of Birkhoff’s theorem in the frame of f(T) gravity via a conformal transformation by regarding the Brans–Dicke-like scalar as effective matter, and study the equivalence between both Einstein frame and Jordan frame.     

Density functional calculations for Rh(I)‐catalyzed C–C bond activation of siloxyvinylcyclopropanes and diazoesters

Density functional theory was employed to investigate rhodium(I)‐catalyzed C–C bond activation of siloxyvinylcyclopropanes and diazoesters. The B3LYP/6‐31G(d,p) level (LANL2DZ(f) for Rh) was used to optimize completely all intermediates and transition states. The computational results revealed that the most favorable pathway was the channel forming the methyl‐branched acyclic product p1 in path A (cyclooctadiene (cod) as the ligand), and the oxidative addition was the rate‐determining step for this channel. It proceeded mainly through the complexation of diazoester to rhodium, rhodium–carbene formation, coordination of siloxyvinylcyclopropane, oxidative addition (C2–C3 bond cleavage) of siloxyvinylcyclopropane, carbene migratory insertion, β‐hydrogen elimination and reductive elimination. The complexation of diazoester to rhodium occurred prior to the coordination of siloxyvinylcyclopropane. Also, the role of the ligands cod, chlorine and 1,4‐dioxane, the effect of di‐rhodium catalyst and the solvent effect are discussed in detail.     

Facile Synthesis of 2H-Benzo[h]Chromenes via an Arylamine-Catalyzed Mannich Cyclization Cascade Reaction

A simple arylamine-catalyzed Mannich-cyclization cascade reaction was developed for facile synthesis of substituted 2H-benzo[h]chromenes. The notable feature of the process included the efficient generation of ortho-quinone methides (o-QMs) catalyzed by a simple aniline. The mild reaction conditions allowed for a broad spectrum of 1- and 2-naphthols and trans-cinnamaldehydes to engage in the cascade sequence with high efficiency.     

Mechanistic Insights into the Interface‐Directed Transformation of Thiols into Disulfides and Molecular Hydrogen by Visible‐Light Irradiation of Quantum Dots

Quantum dots (QDs) offer new and versatile ways to harvest light energy. However, there are few examples involving the utilization of QDs in organic synthesis. Visible‐light irradiation of CdSe QDs was found to result in virtually quantitative coupling of a variety of thiols to give disulfides and H₂ without the need for sacrificial reagents or external oxidants. The addition of small amounts of nickel(II) salts dramatically improved the efficiency and conversion through facilitating the formation of hydrogen atoms, thereby leading to faster regeneration of the ground‐state QDs. Mechanistic studies reveal that the coupling reaction occurs on the QD surfaces rather than in solution and offer a blueprint for how these QDs may be used in other photocatalytic applications. Because no sacrificial agent or oxidant is necessary and the catalyst is reusable, this method may be useful for the formation of disulfide bonds in proteins as well as in other systems sensitive to the presence of oxidants.     

Interchain coupling effects on dynamics of photoexcitations in conjugated polymers

Within an extended Su-Schrieffer-Heeger model including interchain interactions and the extended Hubbard model, the dynamical relaxation of photoexcitations in two coupled conjugated polymer chains is investigated by using a nonadiabatic evolution method. Initially, one of the two chains is photoexcited and the other chain is in the dimerized ground state. Due to the interchain interactions, the electron and/or the hole can be transferred from one chain to the other chain. For weak interchain coupling, the dynamical evolution of the lattice on the photoexcited chain is similar to that found in an isolate single chain case. With interchain interactions increasing, the amplitude of the distortions on the photoexcited chain decreases, and simultaneously, that on the other chain gradually increases. Until stronger interchain coupling, the deformations of the two chains have almost the same amplitude. Besides intrachain polaron-excitons and intrachain oppositely charged polaron pairs as found in single chain case, interchain polaron-excitons and interchain separated charged polaron pairs are obtained. The results show that the yield of interchain products increases and that of intrachain products decreases with interchain coupling increasing. Totally, the yield of charged polarons (including intrachain oppositely charged polaron pairs and interchain oppositely charged polaron pairs) is about 25%, in good agreement with results from experiments.     

Preparation and characterization of thermoplastic elastomer of poly(vinyl chloride) and chlorinated waste rubber

In order to develop applications for the abundant waste rubber powder, chlorinated waste rubber (Cl-WR) was prepared by a water based chlorination method using chlorine as chlorinating agent. In this paper, Cl-WR was used as an elastic filler and blended with poly(vinyl chloride) (PVC) matrix to develop a new thermoplastic elastomer PVC/Cl-WR. The mechanical properties, hydrophilicity, swelling resistance, morphology and thermal properties of PVC/Cl-WR were characterized and compared with those of PVC/waste rubber powder (PVC/WR) blends. The results indicated that the mechanical properties, hydrophilicity, swelling resistance and thermal properties of the PVC/Cl-WR blends showed noticeable improvements over PVC/WR blends due to the improved polarity of Cl-WR. Also, the excellent miscibility and compatibility of Cl-WR with PVC was demonstrated by scanning electron microscope (SEM) images of the resulting blends.     

Synthesis of dendritic polyamide with protected amino functional groups in the periphery

A homologous series of first-to third-generation dendritic polyamides 2a, 3, and 5 with tris(aminoethyl) amine (TREA) as the core and the protected amino functional groups at the periphery were synthesized via active ester route from “Schlüter” type dendron 1a. Their structures were characterized by ¹H-NMR and mass spectra. Based on the efficient synthesis of the first generation dendrimer 2a (yield 75%), the synthesis of second-generation dendrimer 3 was found to be more efficient via the convergent method (yield 69%), while the mixed strategy was applied efficiently for the synthesis of the higher generation dendrimer 5 (yield 37%). The overall yield for the third generation dendrimer 5 from Schlüter dendron is 12%. __________ Translated from Huaxue Tongbao (Chemistry), 2005, 68(12) (in Chinese)     

Exchange frequency in replica exchange molecular dynamics

The effect of the exchange-attempt frequency on sampling efficiency is studied in replica exchange molecular dynamics (REMD). We show that sampling efficiency increases with increasing exchange-attempt frequency. This conclusion is contrary to a commonly expressed view in REMD. Five peptides (1-21 residues long) are studied with a spectrum of exchange-attempt rates. Convergence rates are gauged by comparing ensemble properties between fixed length test REMD simulations and longer reference simulations. To show the fundamental correlation between exchange frequency and convergence time, a simple model is designed and studied, displaying the same basic behavior of much more complex systems.     

Syntheses,Crystal Structures and Luminescent Properties of Three Inorganic‐Organic Hybrid Frameworks Constructed from 4,5‐Imidazoledicarboxylate

Three inorganic‐organic hybrid frameworks [Mn(HIMDC)(4,4′‐bipyo)_0.5(H₂O)]_n (1) , [Cd(H₂IMDC)₂(2,2′‐bipyo)] (2) and [Ca(HIMDC)(H₂O)₂·H₂O]_n (3) (H₃IMDC = 4,5‐imidazoledicarboxylate; 4,4′‐bipyo = 4,4′‐bipyridine‐N,N′‐dioxide; 2,2′‐bipyo= 2,2′‐bipyridine‐N,N′‐dioxide) have been hydrothermally synthesized and characterized by the elemental analyses, IR spectra, TG analysis and the single crystal diffraction. Both compounds 1 and 3 exhibit 2D layers while 2 is a monomer. It is noteworthy that compound 2 exhibits strong fluorescent emission in the solid state at room temperature.