A new approach exploiting thermally activated delayed fluorescence molecules to optimize solar thermal energy storage.

We propose a new concept exploiting thermally activated delayed fluorescence (TADF) molecules as photosensitizers, storage units and signal transducers to harness solar thermal energy. Molecular composites based on the TADF core phenoxazine-triphenyltriazine (PXZ-TRZ) anchored with norbornadiene (NBD) were synthesized, yielding compounds PZDN and PZTN with two and four NBD units, respectively. Upon visible-light excitation, energy transfer to the triplet state of NBD occurred, followed by NBD → quadricyclane (QC) conversion, which can be monitored by changes in steady-state or time-resolved spectra. The small S1-T1 energy gap was found to be advantageous in optimizing the solar excitation wavelength. Upon tuning the molecule's triplet state energy lower than that of NBD (61 kcal/mol), as achieved by another composite PZQN, the efficiency of the NBD → QC conversion decreased drastically. Upon catalysis, the reverse QC → NBD reaction occurred at room temperature, converting the stored chemical energy back to heat with excellent reversibility.

E2f1 regulates the induction of promyelocytic leukemia zinc finger transcription in neuronal differentiation of pluripotent P19 embryonal carcinoma cells.

During brain development, the expression of promyelocytic leukemia zinc finger (Plzf) in neural stem cells is precisely controlled to maintain the balance between neural stem cell self-renewal and differentiation. However, the mechanism underlying transcriptional regulation of Plzf in neural stem cell is still unclear. Herein, using P19 embryonal carcinoma cells as a model, we observed that Plzf expression was induced in the P19-derived embryonic bodies, which enrich neural stem-like cell populations, as demonstrated by the expression of neural stem cell markers, Nestin and Sox2. We then characterized the Plzf promoter and identified two E2f1 binding sites (-755/-751 and -53/-49, the transcription start site was designated as +1) are important for the activation of Plzf promoter. Finally, we found that the induction of Plzf in the neural stem-like cells derived from pluripotent P19 cells is decrease by E2f1 knockdown. Taken together, we conclude that E2f1 is an important transcription factor that regulates Plzf transcription and may involve in maintaining the self-renewal ability of neural stem cells.

Probing the polarity and water environment at the protein-peptide binding interface using tryptophan analogues.

7-Azatryptophan and 2,7-diazatryptophan are sensitive to polarity changes and water content, respectively, and should be ideal for studying protein-protein and protein-peptide interactions. In this study, we replaced the tryptophan in peptide Baa (LKWKKLLKLLKKLLKLG-NH2) with 7-azatryptophan or 2,7-diazatryptophan, forming (7-aza)Trp-Baa and (2,7-aza)Trp-Baa, to study the calmodulin (CaM)-peptide interaction. Dramatic differences in the (7-aza)Trp-Baa and (2,7-aza)Trp-Baa fluorescence properties between free peptide in water and calmodulin-bound peptide were observed, showing a less polar and water scant environment at the binding interface of the peptide upon calmodulin binding. The affinity of the peptides for binding CaM followed the trend Baa (210±10 pM)<(7-aza)Trp-Baa (109±5 pM)<(2,7-aza)Trp-Baa (45±2 pM), showing moderate increase in binding affinity upon increasing the number of nitrogen atoms in the Trp analogue. The increased binding affinity may be due to the formation of more hydrogen bonds upon binding CaM for the Trp analogue with more nitrogen atoms. Importantly, the results demonstrate that (7-aza)Trp and (2,7-aza)Trp are excellent probes for exploring the environment at the interface of protein-peptide interactions.

Acrothoracican barnacles (Lithoglyptida) in Taiwan, including the taxonomic status of Balanodytes taiwanus Utinomi, 1950 and cryptic diversity of Auritoglyptes bicornis (Aurivillius, 1892).

We list five acrothoracican barnacles of the order Lithoglyptida currently found in Taiwanese waters, including two new records, Trypetesa habei Utinomi, 1962 and Berndtiapurpurea Utinomi, 1950 and a new undescribed species of the genus Lithoglyptes. We also investigate the morphology and molecular genetics of Balanodytes taiwanus Utinomi, from its type locality, Taiwan. The original description of B. taiwanus in Utinomi (1950a) reported the absence of caudal appendages. Re-examination of the somatic body of one of the syntype specimens (the other syntype only having an opercular bar remaining) of B. taiwanus deposited in the Seto Marine Laboratory in Japan, revealed the presence of caudal appendages. The morphology of our specimens collected in various locations in Taiwan fits the description in Utinomi (1950a) and all have caudal appendages. The diagnosis of Balanodytes Utinomi, 1950 is revised herein. The genus Armatoglyptes Kolbasov & Newman, 2005 is a nomen nudum and ajunior synonym of Balanodytes. Our results also show that the widespread species Lithoglyptes habei Tomlinson, 1963 is a junior synonym of B. taiwanensis. The molecular sequence divergencse of the 16S RNA and COI genes were studied for samples of another monotypic genus Auritoglyptes (A. bicornis) from different regions of Taiwan. It was shown that there are at least three phylogenetic clades in Taiwan, suggesting that Auritoglyptes represents a cryptic species complex.

Five related metal-organic frameworks constructed from [Ln2(SO4)2(H2O)n]2+ units and oxalate or acetate ligands.

We have synthesized a series of lanthanide-based metal-organic solids and characterized them through structural, magnetic and luminescence analyses. The nine compounds in the series NH(4)[Ln(SO(4))(H(2)O)(C(2)O(4))] [Ln = Ce, Nd, Eu, Gd (x2), Tb, Dy, Er, Yb] belong to four new three-dimensional (3D) structural groups, which we label CKMOF-4a, -4b, -5a, and -5b. The CKMOF-4a (Ce.) and -4b (Gd., Tb., Dy., Er., Yb.) structures feature [Ln(2)(SO(4))(2)(H(2)O)(2)](2+) units and C(2)O(4)(2-) ligands having the same symmetry operations, but their SO(4)(2-) anions feature different connective modes. These units are extended into one-dimensional ribbons fused together by oxalate ligands to form the two 3D open frameworks. The structures of CKMOF-5a (Nd.) and -5b (Eu., Gd.) comprise networks of c-glide-arranged [Ln(2)(SO(4))(2)(H(2)O)(2)](2+) units, in which the oxalate ligands are encapsulated within eight-membered rings. The networks are supported by distinct sites of oxalate ligands to form the two types of 3D open frameworks, the structural topologies of which are distinguished by the versatile connective modes of the SO(4)(2-) anions. The polymeric phases CKMOF-4b and -5b exist in the Gd analogues. For the Dy analogues, varying the size of the cation used as the template led to the selective precipitation of each of these two phases. The layer structure of [Gd(SO(4))(H(2)O)(2)(CH(3)CO(2))] (Gd.), labelled CKMOF-6, assembled from [Gd(2)(SO(4))(2)(H(2)O)(4)](2+) units and acetate ligands; the geometries of the [Gd(2)O(2)] rhombic units may induce ferromagnetic coupling at low temperature. Eu. and Tb. were luminescent, displaying red and green emissions, respectively.

The surface modification of silver nanoparticles by phosphoryl disulfides for improved biocompatibility and intracellular uptake.

In order to enhance the biocompatibility and cell affinity of metal nanoparticles for biosensing and drug delivering applications, we prepared the phospholipid derivatives containing disulfide groups to modify silver nanoparticle surfaces. By adding sodium borohydride to reduce both disulfide bonds of the derivatives and silver ions simultaneously, the generated thiol groups can be reacted with newborn silver atoms immediately to generate nanoclusters. The assemblies consisted of either phosphorylcholine (PC) or phosphorylethanolamine (PE) head groups, which made the silver clusters biocompatibile. Transmission electron microscope (TEM) and optical absorption spectra assisted in modulating reaction conditions, demonstrating that a surfactant/Ag ratio of 0.4 led to the formation of uniform, well-dispersed spherical particles about 3.8 nm in diameter. X-ray photoelectron spectra and infrared spectra also illustrated the elemental and molecular structures of nanoparticles. The insertion of rhodamine dye into the surfactant layer enabled the nanoparticles to be used as a fluorescent probe. In cell culture tests, the nanoparticles were internalized into platelet or fibroblast cells in a short period of incubation without harming the cells.

Effect of chelating functional polymer on the size of CdS nanocluster formation.

Chelating poly(acrylates-co-2-methylacrylic acid 3-(bis-carboxymethylamino)-2-hydroxy-propyl ester) microspheres of diameter 250-310 nm were prepared by the soap-free emulsion polymerization method for varying amounts of GMA-IDA. Then CdS/copolymer composite was generated by chemical deposition on the surface of the copolymer microspheres. By XRD analysis it is found that the chelated CdS nanoparticles are a pure cubic zinc blende structure. The CdS/copolymer composite is examined by UV-vis absorbance, photoluminescence, and TEM observation. Average CdS nanoparticle size calculated from Henglein's empirical curve is in the range of 3.0-8.0 nm and varies according to the GMA-IDA molar ratio during polymerization, pH value during chelation, and postchelation annealing temperature. Higher ratio of chelating group, pH value, and annealing temperature produce larger CdS nanoparticles. As GMA-IDA ratio increases, photoluminescence exhibits a red shift from 510 to 520 nm, photoluminescence increases, and bandwidth decreases. Photoluminescence of the CdS nanoparticle becomes negligible when diameter exceeds 5 nm.