Smart Approach for In Situ One‐Step Encapsulation and Controlled Delivery of a Chemotherapeutic Drug using Metal–Organic Framework–Drug Composites in Aqueous Media

Controlled release of an anticancer drug, doxorubicin (dox), from metal–organic framework (MOF)–drug composites is demonstrated under different external stimuli. 1,3,5‐Benzenetricarboxylic acid (H₃BTC) is used as an organic ligand, and iron acetate and zinc nitrate are used as metal sources to synthesize Fe–BTC and Zn–BTC MOFs, which are known to be biocompatible. The in situ formation of MOF–drug composites demonstrates high drug loading capacity compared to conventional methods. The present methodology is devoid of any extra steps for loading the drug after synthesis. Moreover, the drug loading is also independent of pore size of the MOF as the drug molecules are embedded inside the MOF during their in situ formation. The drug release was monitored under external stimuli including change to acidic pH and the presence of biocompatible liposomes for a period of more than 72 h. Steady‐state fluorescence spectroscopy is used to monitor the drug release as a function of time and confocal laser scanning microscopy is used to unravel the post‐release fate of doxorubicin in the presence of liposomes. It is found that drug release rate is higher for the Zn–BTC–dox composite than for the Fe–BTC–dox composite. This is attributed to the stronger binding between dox and Fe‐BTC than that between dox and Zn–BTC. This study highlights a novel approach for the preparation of MOF–drug composites in an aqueous medium for future biomedical applications.     

Space-time contours to treat intense field-dressed molecular states. II. Applications

This second article in the two back-to-back articles presents a numerical application to support and strengthen two theoretical findings extensively discussed in the previous article (article I). In I, we found that introducing the space-time contours enables to distinguish between N, the number of nuclear Schrodinger equations to be solved, and L, the number of field-free states that become populated by the external field (in the ordinary, perturbative approaches this distinction is not apparent). In the numerical study we show, employing the electronic transition probability matrix P(s,t) [which closely is related to the transformation matrix omega(s,t)--see Eqs. (21) and (25) in I], that the N=L case is rare and in most cases we have N相似文献   

Microwave-Assisted Enzymatic Extraction of Flavonoids from Armeniaca mume Sieb. Blossom and Their Immunomodulating Effect in Mice with DSS-Induced Colitis

Armeniaca mume Sieb. blossom is among the traditional Chinese edible flowers, and it is widely used in the food and pharmaceutical industries. Flavonoids are among the most abundant bioactive compounds in A. mume Sieb. blossom. However, the research on the extraction of flavonoids from A. mume Sieb. blossom and their immunomodulating function is insufficient. In this study, we developed a microwave-assisted enzymatic extraction of flavonoids from A. mume Sieb. blossom (FAMB) and explored their immunomodulating effect on mice with dextran sulfate sodium salt-induced colitis. The results showed that the optimum parameters for microwave-assisted enzymatic extraction of FAMB were as follows: cellulase: 2.0%; microwave power: 200 W; microwave action time: 5 min; and enzymatic hydrolysis time: 50 min. FAMB significantly promoted the lymphocyte proliferation and natural killer (NK) cell killing activity in colitis mice, and increased the concentrations of TNF-α, IFN-γ, and IL-2 in serum. FAMB also significantly reduced the apoptosis of spleen lymphocytes in these mice. These results demonstrated that the microwave-assisted enzymatic method could significantly improve the yield and efficacy extraction of FAMB. FAMB showed a good immunomodulation effect on colitis mice.     

Luminescence,Plasmonic, and Magnetic Properties of Doped Semiconductor Nanocrystals

Introducing a few atoms of impurities or dopants in semiconductor nanocrystals can drastically alter the existing properties or even introduce new properties. For example, mid-gap states created by doping tremendously affect photocatalytic activities and surface controlled redox reactions, generate new emission centers, show thermometric optical switching, make FRET donors by enhancing the excited state lifetime, and also create localized surface plasmon resonance induced low energy absorption. In addition, researchers have more recently started focusing their attention on doped nanocrystals as an important and alternative material for solar energy conversion to meet the current demand for renewable energy. Moreover, the electrical and magnetic properties of the host are also strongly altered on doping. These beneficial dopant-induced changes suggest that doped nanocrystals with proper selections of dopant–host pairs may be helpful for generating designer materials for a wide range of current technological needs. How properties relate to the doping of a variety of semiconductor nanocrystals are summarized in this Review.     

Ultrafast proton transfer of pyranine in a supramolecular assembly: PEO-PPO-PEO triblock copolymer and CTAC

Excited-state proton transfer (ESPT) of pyranine (8-hydroxypyrene-1,3,6-trisulfonate, HPTS) is studied in a polymer-surfactant aggregate using femtosecond emission spectroscopy. The polymer-surfactant aggregate is a supramolecular assembly consisting of a triblock copolymer (PEO)(20)-(PPO)(70)-(PEO)(20) (P123) and a cationic surfactant, cetyltrimethylammonium chloride (CTAC). ESPT of the protonated species (HA) in HPTS leads to the formation of A(-). The dynamics of ESPT may be followed from the decay of the HA emission (at approximately 440 nm) and rise of the A(-) emission (at approximately 550 nm). Both steady-state and time-resolved studies suggest that ESPT of HPTS in P123-CTAC aggregate is much slower than that in bulk water, in P123 micelle, or in CTAC micelle. The ratio of the steady-state emission intensities (HA/A(-)) in P123-CTAC aggregate is 2.2. This ratio is approximately 50, 12, and 2 times higher than that respectively in water, in P123 micelle, and in CTAC micelle. Retardation of ESPT causes an increase in the rise time of the A(-) emission of HPTS. In P123-CTAC aggregate, A(-) displays three rise times: 30, 250, and 2400 ps. These rise times are longer than those in CTAC micelle (23, 250, and 1800 ps), in bulk water (0.3, 3, and 90 ps), and in P123 micelle (15 and 750 ps). The rate constants for initial proton transfer, recombination, and dissociation of the ion pair are estimated using a simple kinetic scheme. The slow fluorescence anisotropy decay of HPTS in P123-CTAC aggregate is analyzed in terms of the wobbling-in-cone model.     

Formation of Highly Ordered Molecular Porous 2D Networks from Cyano-Functionalized Porphyrins on Cu(111)

We investigated the adsorption of three related cyano-functionalized tetraphenyl porphyrin derivatives on Cu(111) by scanning tunneling microscopy (STM) in ultra-high vacuum (UHV) with the goal to identify the role of the cyano group and the central Cu atom for the intermolecular and supramolecular arrangement. The porphyrin derivatives studied were Cu-TCNPP, Cu-cisDCNPP, and 2H-cisDCNPP, that is, Cu-5,10,15,20-tetrakis-(p-cyano)-phenylporphyrin, Cu-meso-cis-di(p-cyano)-phenylporphyrin and 2H-meso-cis-di(p-cyano)-phenylporphyrin, respectively. Starting from different structures obtained after deposition at room temperature, all three molecules form the same long-range ordered hexagonal honeycomb-type structure with triangular pores and three molecules per unit cell. For the metal-free 2H-cisDCNPP, this occurs only after self-metalation upon heating. The structure-forming elements are pores with a distance of 3.1 nm, formed by triangles of porphyrins fused together by cyano-Cu-cyano interactions with Cu adatoms. This finding leads us to suggest that two cyano-phenyl groups in the “cis” position is the minimum prerequisite to form a highly ordered 2D porous molecular pattern. The experimental findings are supported by detailed density functional theory calculations to analyze the driving forces that lead to the formation of the porous hexagonal honeycomb-type structure.     

Remarks on some zero-sum problems

Let Z denote the ring of integers and for a prime p and positive integers r and d, let f_r(P, d) denote the smallest positive integer such that given any sequence of f_r(p, d) elements in (Z/pZ(^d, there exists a subsequence of (rp) elements whose sum is zero in (Z/pZ(^d. That f₁(p, 1) = 2p − 1, is a classical result due to Erdős, Ginzburg and Ziv. Whereas the determination of the exact value of f₁(p, 2) has resisted the attacks of many well known mathematicians, we shall see that exact values of f_r(p, 1) for r ≥ 1 can be easily obtained from the above mentioned theorem of Erdős, Ginzburg and Ziv and those of f_r(p, 2) for r ≥ 2 can be established by the existing techniques developed by Alon, Dubiner and Rónyai in connection with obtaining good upper bounds for f₁(p, 2). We shall also take this opportunity to describe some of the early results in the introduction.     

ZnO-CNT composite nanotubes as nanoresonators

This Letter reports the very first vibration analysis of the novel composite nanotubes (NTs) synthesized by coating carbon nanotubes (CNTs) with piezoelectric zinc oxide (ZnO). Timoshenko beam theory was used and modified to account for the interlayer van der Waals (vdW) interaction in the inner CNT and hybrid structures of the NTs. The distinctive vibration behaviours of the NTs were captured and the physics behind these unique features was investigated in terms of the critical role of the vdW interaction and the effect of the ZnO coating layer on the structural rigidity of the NTs. The composite NTs are found to be promising for gigahertz/terahertz electromechanical nanoresonators whose frequency can be even higher than that of the core CNTs.     

Vibration of ZnO nanotubes: a molecular mechanics approach

We investigate the vibrational properties of two kinds of single-wall ZnO nanotubes. The simulations are carried out for three types of zigzag nanotubes (5,0), (8,0), (10,0) and armchair nanotubes (3,3), (4,4), (6,6). The natural frequencies are determined by means of the molecular mechanics approach with the universal force field potential. The first four natural frequencies are obtained for length/diameter ratio of about 5–20. The vibration modes associated with these frequencies have been computed. Closed-form analytical expressions have been derived using the continuum shell theory for the physical explanations of the simulations results. We observe that the natural frequencies decrease as the aspect ratios increase. The results follow similar trends with results of previous studies for carbon nanotubes (CNT). However, the magnitudes of the frequencies are lower from the corresponding CNT counterparts, indicating that ZnO nanotubes are comparatively less stiff.