Preparation and Characterization of Pt/Co‐Core Au‐Shell Magnetic Nanoparticles

Pt/Co‐core Au‐shell nanoparticles were synthesized via a two‐step route using NaBH₄ as a reducing agent. The nanoparticles are characterized by UV‐vis spectroscopy, transmission electron microscopy (TEM) and powder X‐ray diffraction (XRD). The results indicate that the as‐synthesized Pt/Co‐core Au‐shell nanoparticles have a disordered face centered cubic (fcc) structure, whereas the annealed Pt/Co‐core Au‐shell nanoparticles exhibit an ordered face centered tetragonal (fct) structure. Superconducting quantum interference device (SQUID) studies reveal that the coercivity of the annealed Pt/Co‐core Au‐shell nanoparticles increases to 510 Oe after heat treatment at 500 °C for 2 h.     

Surface‐Imprinted,Thermosensitive, Core‐Shell Nanosphere for Molecular Recognition

Summary: The D ‐glucose imprinted core‐shell nanosphere with an average size of ≈60 to 80 nm showed a significant preference for the binding of D ‐glucose than the non‐imprinted core‐shell nanosphere. Depending on temperature, the binding site in the shell with N‐isopropylacrylamide oligomer underwent a significant change in binding affinity. In addition, the D ‐glucose imprinted core‐shell nanosphere showed a two times higher affinity for D ‐glucose than L ‐glucose, suggesting chiral recognition of the binding site. The core‐shell nanosphere reported here is a good biomimetic model system with a well‐defined morphology, high surface area, and variable binding affinity through a change in temperature.

D ‐glucose imprinted core‐shell nanospheres showed excellent binding over the non‐imprinted core‐shell nanosphere.     

From Open‐Shell Singlet Diradicaloid to Closed‐Shell Global Antiaromatic Macrocycles

A dithieno[a,h]‐s‐indacene‐ (DTI‐) based diradicaloid DTI‐2Br was synthesized and its open‐shell singlet diradical character was validated by magnetic measurements. On the other hand, its macrocyclic trimer DTI‐MC3 and tetramer DTI‐MC4 turned out to be closed‐shell compounds with global antiaromaticity, which was supported by X‐ray crystallographic analysis and NMR spectroscopy, assisted by ACID and 2D‐ICSS calculations. Such change can be explained by a subtle balance between two types of antiferromagnetic spin–spin coupling along the π‐conjugated macrocycles. The dications of DTI‐MC3 and DTI‐MC4 turned out to be open‐shell singlet diradical dications, with a singlet–triplet energy gap of ?2.90 and ?2.60 kcal mol^?1, respectively. At the same time, they are both global aromatic. Our studies show that intramolecular spin–spin interactions play important roles on electronic properties of π‐conjugated macrocycles.     

Surface‐State‐Mediated Charge‐Transfer Dynamics in CdTe/CdSe Core–Shell Quantum Dots

Herein, we report the synthesis of aqueous CdTe/CdSe type‐II core–shell quantum dots (QDs) in which 3‐mercaptopropionic acid is used as the capping agent. The CdTe QDs and CdTe/CdSe core–shell QDs are characterized by X‐ray diffraction (XRD), high‐resolution transmission electron microscopy (HR‐TEM), steady‐state absorption, and emission spectroscopy. A red shift in the steady‐state absorption and emission bands is observed with increasing CdSe shell thickness over CdTe QDs. The XRD pattern indicates that the peaks are shifted to higher angles after growth of the CdSe shell on the CdTe QDs. HR‐TEM images of both CdTe and CdTe/CdSe QDs indicate that the particles are spherical, with a good shape homogeneity, and that the particle size increases by about 2 nm after shell formation. In the time‐resolved emission studies, we observe that the average emission lifetime (τ_av) increases to 23.5 ns for CdTe/CdSe (for the thickest shell) as compared to CdTe QDs (τ_av=12 ns). The twofold increment in the average emission lifetime indicates an efficient charge separation in type‐II CdTe/CdSe core–shell QDs. Transient absorption studies suggest that both the carrier cooling and the charge‐transfer dynamics are affected by the presence of traps in the CdTe QDs and CdTe/CdSe core–shell QDs. Carrier quenching experiments indicate that hole traps strongly affect the carrier cooling dynamics in CdTe/CdSe core–shell QDs.     

Ultra‐small,Uniform, and Single bcc‐Phased FexCo1‐x/Graphitic Shell Nanocrystals for T1 Magnetic Resonance Imaging Contrast Agents

We have synthesized ultra‐small and uniform Fe_xCo_1‐x/graphitic carbon shell (Fe_xCo_1‐x/GC) nanocrystals (x=0.13, 0.36, 0.42, 0.50, 0.56, and 0.62, respectively) with average diameters of <4 nm by thermal decomposition of metal precursors in approximately 60 nm MCM‐41 and methane CVD. The composition of the Fe_xCo_1‐x/GC nanocrystals can be tuned by changing the Fe:Co ratios of the metal precursors. The Fe_xCo_1‐x/GC nanocrystals show superparamagnetic properties at room temperature. The Fe_0.50Co_0.50/GC, Fe_0.56Co_0.44/GC, and Fe_0.62Co_0.38/GC nanocrystals have a single bcc FeCo structure, whereas the Fe_0.13Co_0.87/GC, Fe_0.36Co_0.64/GC, and Fe_0.42Co_0.58/GC nanocrystals have a mixed structure of bcc FeCo and fcc Co. The single bcc‐phased Fe_xCo_1‐x/GC nanocrystals functionalized with phospholipid–poly(ethylene glycol) (PL–PEG) in phosphate buffered saline (PBS) are demonstrated to be excellent T₁ MRI contrast agents.     

Laser Assisted Catalytic Growth of ZnS/CdSe Core‐Shell and Wire‐Coil Nanowire Heterostructures

ZnS/CdSe core‐shell and wire‐coil nanowire heterostructures have been synthesized by chemical vapor deposition assisted with pulsed laser ablation. Measurements from high‐resolution transmission electron microscopy and selected area electron diffraction have revealed that both ZnS/CdSe core‐shell and wire‐coil nanowires are of single‐crystalline hexagonal wurtzite structures and grow along the [0001] direction. While the lattice parameters of ZnS and CdSe in the core‐shell nanowires are nearly equal to those of bulk ZnS and CdSe, change of the lattice parameters in the CdSe‐coil is attributed to the doping of Zn into CdSe, resulting in the relaxation of compressive strain at the interface between CdSe‐coil and ZnS‐wire. Composition variation across the interfacial regions in the ZnS/CdSe nanowire heterostructures ranges only 10–15 nm despite the pronounced lattice mismatch between ZnS and CdSe by ?11%. Growth mechanisms of the ZnS/CdSe nanowire heterostructures are discussed.     

Synthesis of Multifunctional Mn‐Doped CdTe/ZnS Core/Shell Quantum Dots

The synthesis of a novel water‐soluble Mn‐doped CdTe/ZnS core‐shell quantum dots using a proposed ultrasonic assistant method and 3‐mercaptopropionic acid (MPA) as stabilizer is descried. To obtain a high luminescent intensity, post‐preparative treatments, including the pH value, reaction temperature, reflux time and atmosphere, have been investigated. For an excellent fluorescence of Mn‐doped CdTe/ZnS, the optimal conditions were pH 11, reflux temperature 100°C and reflux time 3 h under N₂ atmosphere. While for phosphorescent Mn‐doped CdTe/ZnS QDs, the synthesis at pH 11, reflux temperature 100°C and reflux time 3 h under air atmosphere gave the best strong phosphorescence. The characterizations of Mn‐doped CdTe/ZnS QDs were also identified using AFM, IR, powder XRD and thermogravimetric analysis. The data indicated that the photochemical stability and the photoluminescence of CdTe QDs are greatly enhanced by the outer inorganic ZnS shell, and the doping Mn²⁺ ions in the as‐prepared quantum dots contribute to strong luminescence. The strong luminescence of Mn‐doped CdTe/ZnS QDs reflected that Mn ions act as recombination centers for the excited electron‐hole pairs, attributing to the transition from the triplet state (⁴T₁) to the ground state (⁶A₁) of the Mn²⁺ ions. All the experiments demonstrated that the surface states played important roles in the optical properties of Mn‐doped CdTe/ZnS core‐shell quantum dots.     

Switching of Redox Properties Triggered by a Thermal Equilibrium between Closed‐Shell Folded and Open‐Shell Twisted Species

Thermally switchable redox properties have been reported to be due to a change in the spin state of newly designed overcrowded ethylenes, which can adopt closed‐shell folded and open‐shell twisted forms. In this study, tetrathienylanthraquinodimethane derivatives were designed to be in thermal equilibrium between a more stable folded form and less stable but more donating twisted diradical in solution, so that the oxidation potential can be controlled by heating/cooling. This is the first example of a switching of redox properties based on a thermally equilibrated twisted diradical, which can be more readily oxidized to the twisted dication.     

Synthesis and Characterization of Core‐Shell Selenium/Carbon Colloids and Hollow Carbon Capsules

A novel Se/C nanocomposite with core‐shell structures has been prepared through a facile one‐pot microwave‐induced hydrothermal process. The new material consists of a trigonal‐Se (t‐Se) core and an amorphous‐C (a‐C) shell. The Se/C composite can be converted to hollow carbon capsules by thermal treatment. These products were characterized by transmission electron microscopy (TEM), powder X‐ray diffraction (XRD), scanning electron microscopy (SEM), selected area electron diffraction (SAED), energy‐dispersive X‐ray (EDX) spectroscopy, and X‐ray photoelectron spectroscopy (XPS).     

Three‐Dimensional Ordered Assembly of Thin‐Shell Au/TiO2 Hollow Nanospheres for Enhanced Visible‐Light‐Driven Photocatalysis

An Au/TiO₂ nanostructure was constructed to obtain a highly efficient visible‐light‐driven photocatalyst. The design was based on a three‐dimensional ordered assembly of thin‐shell Au/TiO₂ hollow nanospheres (Au/TiO₂‐3 DHNSs). The designed photocatalysts exhibit not only a very high surface area but also photonic behavior and multiple light scattering, which significantly enhances visible‐light absorption. Thus Au/TiO₂‐3 DHNSs exhibit a visible‐light‐driven photocatalytic activity that is several times higher than conventional Au/TiO₂ nanopowders.