Spatial and temporal regulations of ATRP by external stimuli are presented. Various ATRP techniques, eATRP, photoATRP, and mechanoATRP, are controlled by electrical current, light, and mechanical forces, respectively. Conversely, ARGET and SARA ATRP are controlled by chemical reducing agents. ICAR ATRP is a thermally regulated process through decomposition of a radical initiator. The aim of this review is to highlight the use of external regulations in ATRP and to summarize the state-of-the-art and future perspectives, focusing on mechanistic aspects, synthetic procedures, preparation of polymers with complex architectures and functional materials, and their applications.

Computationally-efficient semilocal approximations of density functional theory at the level of the local spin density approximation (LSDA) or generalized gradient approximation (GGA) poorly describe weak interactions. We show improved descriptions for weak bonds (without loss of accuracy for strong ones) from a newly-developed semilocal meta-GGA (MGGA), by applying it to molecules, surfaces, and solids. We argue that this improvement comes from using the right MGGA dimensionless ingredient to recognize all types of orbital overlap.PACS numbers: 34.20.Gj, 31.15.E-, 87.15.ADue to its computational efficiency and reasonable accuracy, the Kohn-Sham density functional theory [1][2][3] with semilocal approximations to the exchangecorrelation energy, e.g., the local spin density approximation (LSDA) [4,5] and the standard Perdew-BurkeErnzerhof (PBE) generalized gradient approximation (GGA) [6], is one of the most widely-used electronic structure methods in materials science, surface science, condensed matter physics, and chemistry. Semilocal approximations display a well-understood error cancellation between exchange and correlation in bonding regions. Thus some intermediate-range correlation effects, important for strong and weak bonds, are carried by the exchange part of the approximation. However, it is well-known that these approximations cannot yield correct long-range asymptotic dispersion forces [7]. This raises doubts about the suitability of semilocal approximations for the description of weak interactions (including hydrogen bonds and van der Waals interactions), even near equilibrium where most interesting properties occur. These doubts are supported by the performance of LSDA and GGAs, which are not very useful for many important systems and properties (such as DNA, physisorption on surfaces, most biochemistry, etc.).However, these doubts are challenged by recent developments in semilocal meta-GGAs (MGGA) [8][9][10][11][12][13][14] (which are useful by themselves and as ingredients of hybrid functionals [14]). Compared to GGAs, which use the density n(r) and its gradient ∇n as inputs, MGGAs additionally include the positive kinetic energy density τ = k |∇ψ k | 2 /2 of the occupied orbitals ψ k . For simplicity, we suppress the spin here. By including training sets of noncovalent interactions, the moleculeoriented and heavily-parameterized M06L MGGA was trained to capture medium-range exchange and correlation energies that dominate equilibrium structures of noncovalent complexes [9]. Madsen et al. showed that the inclusion of the kinetic energy densities enables MGGAs to discriminate between dispersive and covalent interactions, which makes the M06L MGGA [9] suitable for layered materials bonded by van der Waals interactions [15,16]. Besides improvement for noncovalent bonds, simultaneous improvement for metallic and covalent bonds is also an outstanding problem for semilocal functionals [17,18]. Ref. 18 has shown that the revised Tao-Perdew-Staroverov-Scuseria (revTPSS) [10] MGGA, due to the inclusion of ...

Photodynamic therapy (PDT) is a promising singlet oxygen ((1)O2) mediated clinical treatment for many tumors. As the source of (1)O2, oxygen plays an important role in the curative effect of PDT. However, the facts of photochemical depletion of oxygen and the intrinsic hypoxic microenvironment of tumors remain the major challenges. In this work, a novel photosensitizer carrier with oxygen self-compensating ability was designed for PDT. It was synthesized via chemical conjugation of hemoglobin (Hb) to polymeric micelles formed by triblock copolymers of poly(ethylene glycol)-block-poly(acrylic acid)-block-polystyrene (PEG-b-PAA-b-PS). The PEG-b-PAA-b-PS and resultant micelles in aqueous solution were comprehensively characterized by means of FTIR, (1)H NMR, GPC, DLS, TEM, and fluorescence spectroscopy. The oxygen-binding capacity and antioxidative activity of the Hb conjugated micelles were evaluated via UV-vis spectroscopy. In addition, compared with the control micelles without Hb, the Hb conjugated photosensitizer carrier was able to generate more (1)O2 and exert greater photocytotoxicity on Hela cells in vitro.

In a standard Kohn-Sham density functional calculation, the total energy of a crystal at zero temperature is evaluated for a perfect static lattice of nuclei, and minimized with respect to the lattice constant. Sometimes a zero-point vibrational energy, whose anharmonicity expands the minimizing or equilibrium lattice constant, is included in the calculation or (as here) used to correct the experimental reference value for the lattice constant to that for a static lattice. A simple model for this correction, based on the Debye and Dugdale-MacDonald approximations, requires as input only readily-available parameters of the equation of state, plus the experimental Debye temperature. However, due in particular to the rough Dugdale-MacDonald estimation of Grüneisen parameters for diatomic solids, this simple model is found to overestimate the correction by about a factor of two for some solids in the diamond and zinc-blende structures. Using the quasi-harmonic phonon frequencies calculated from density functional perturbation theory gives a more accurate zero-point anharmonic expansion (ZPAE) correction. The error statistics for the lattice constants of various semilocal density functionals for the exchange-correlation energy are however little changed by improving the ZPAE correction. The PerdewBurke-Ernzerhof generalized gradient approximation (GGA) for solids (PBEsol) and the revised TaoPerdew-Staroverov-Scuseria (revTPSS) meta-GGA, the latter implemented here selfconsistently in BAND, applied to a test set of 58 solids, remain the most accurate of the functionals tested, with mean absolute relative errors below 0.7% for the lattice constants. The most positive and most negative revTPSS relative errors tend to occur for solids where full nonlocality (missing from revTPSS) may be most important.

We report a facile strategy for quickly fabricating thermosensitive poly(HPMA-co-NVP) hydrogels in the presence of glycerol by using frontal polymerization (FP). The appropriate amounts of hydroxypropyl methacrylate (HPMA) and 1-vinyl-2-pyrrolinone (NVP), N,N 0 -methylenebisacrylamide (MBAA), and ammonium persulfate (APS)/N,N,N 0 ,N 0 -tetramethylethylenediamine (TMEDA) couple redox initiator were mixed together at ambient temperature in the presence of glycerol as the medium. A variety of features for preparing hydrogel samples, such as ratios of NVP/ HPMA, the presence of the glycerol and its concentration, and MBAA cross-linker concentration, were thoroughly investigated. We have found that the presence of glycerol can suppress the "fingering" of FP and overcome the formation of bubbles. Also, the ratio of NVP/HPMA for synthesis of hydrogels by FP plays an important role in its microstructure and swelling property. The morphology, thermosensitive behavior, and swelling studies of polymer hydrogels prepared via FP are comparatively investigated on the basis of environmental scanning electron microscopy (ESEM) and swelling measurement. Results show that the swelling capacity of the hydrogel prepared via FP is superior to that obtained by the traditional batch polymerization (BP) method. The glycerol-assisted FP can be exploited as an alternative means for synthesis of NVP-based copolymer hydrogels with additional advantages of fast and efficient way.

Knowledge of atomistic structures at solid/liquid interfaces is essential to elucidate interfacial processes in chemistry, physics, and materials sciences. The (Ö3´Ö7) structure associated with a pair of sharp reversible current spikes in the cyclic voltammogram on a Au(111) electrode in sulfuric acid solution, represents one of the most classical structures at electrode/electrolyte interfaces. Although more than ten adsorption configurations have been proposed by more than ten groups in the past four decades, the atomistic structure remains ambiguous and is consequently an open problem in electrochemistry and surface science. Herein, by combining high-resolution electrochemical scanning tuning microscopy, electrochemical infrared and Raman spectroscopies, and in particular, the newly developed quantitative computational method for electrochemical infrared and Raman spectra, we unambiguously reveal that the adstructure is Au(111)(Ö3´Ö7)-(SO4•••w2) with a sulfate anion (SO4*) and two structured-water molecules (w2*) in a unit cell, and the crisscrossed [w•••SO4•••w]n and [w•••w•••]n hydrogen-bonding network comprises the symmetric adstructure. We further elucidate that the electrostatic potential energy dictates the proton affinity of sulfate anions, leading to the potential-tuned structural transformations. Our work enlightens the structural details of the inner Helmholtz plane and thus advances our fundamental understanding of the processes at electrochemical interfaces.

Herein, a sensitive and selective sensor for mercury(II) and glutathione based on the aggregation-induced emission (AIE) of a tetraphenylethene derivative stimulated by Hg(2+)-DNA complexes is reported. Aggregation complexes of AIE probes, quaternized tetraphenylethene salt and anti-Hg(2+) aptamer ssDNA, were formed based on the electrostatic interactions between the ammonium cation of AIE probes and the backbone phosphate anions of DNA. In the presence of target Hg(2+), the aptamer ssDNA with thymine (T)-rich sequences selectively bound with Hg(2+) to form an Hg(2+)-bridged T base pair and the ssDNA changed into a hairpin-like structure. Therefore the AIE probing molecules were brought to be positioned closer. Accordingly, the conformational change of aptamer ssDNA resulted in an obvious enhancement in the fluorescence of the probing complex enabling the sensitive and selective detection of Hg(2+). Furthermore, upon reaction of Hg(2+) with biothiols, the compact structure was destroyed and the fluorescence decreased consequently. Sensitive detection of GSH was realised based on the decrease of fluorescence of the probing complex. The target-aptamer complexes stimulating aggregation-induced emission therefore show great promise for environmental and biological process monitoring and disease diagnosis.

An alkaline phosphatase activity detection system was constructed based on the different quenching effect of the enzyme substrate and product on the β-CD-functionalized CdTe QDs.