An ultralong room-temperature phosphorescent material based on the combination of small singlet-triplet splitting energy and H-aggregation.

Compound AI-N-Cz was conveniently synthesized, and it exhibited ultralong room-temperature phosphorescence (RTP) with a lifetime of 775 ms, which was more than 400 times the RTP lifetime of its isomer AI-Cz (1.9 ms). The ultralong RTP of AI-N-Cz might be due to the combination of small singlet-triplet splitting energy (ΔEST) and H-aggregation, and this could be an efficient strategy for the further design of ultralong organic room-temperature materials.

Phthalimide-based "D-N-A" emitters with thermally activated delayed fluorescence and isomer-dependent room-temperature phosphorescence properties.

Phthalimide-based "D-N-A" emitters o-AI-Cz, m-AI-Cz and p-AI-Cz showed TADF and RTP properties due to their small ΔEST in both film and crystalline states. In particular, o-AI-Cz exhibited an ultralong RTP with a lifetime of 602 ms in air and remarkable afterglow, which could allow it to be used as a security ink for application in anti-counterfeiting materials. Moreover, o-AI-Cz showed intense intramolecular interaction between the donor and the acceptor subunits, while p-AI-Cz could form regular hexagonal pores with a diameter of 13.171 Å in the solid state, which might result in their different RTP properties.

A fast 3-D ultrasound projection imaging method for scoliosis assessment.

Applying ultrasound for scoliosis assessment has been an attractive topic over the past decade. This study proposed a new fast 3-D ultrasound projection imaging method to evaluate the spine deformity. A narrow-band rendering method was used to generate the coronal images based on B-mode images and their corresponding positional data. The non-planar reslicing method, which followed the natural spine curve, was used to project the complete spine data into the coronal image. The repeatability of the new method was tested. A comparison experiment on the reconstructed images and the processing time between the conventional 3-D rendering method and the developed projection imaging method was also performed among 70 patients with scoliosis. The intra- and inter-operator tests results demonstrated very good repeatability (ICC ≥ 0.90). The mean processing times for the developed projection method and conventional rendering method were 15.07 ± 0.03 s and 130.31 ± 35.07 s, respectively. The angle measurement results showed a high correlation (y = 0.984x, r = 0.954) between the images obtained using the two methods. The above results indicated that the developed projection imaging method could greatly decrease the processing time while preserving the comparative image quality. It can be expected that this novel method may help to provide fast 3-D ultrasound diagnosis of scoliosis in clinics.

Solvent-Controlled Synthesis of Highly Luminescent Carbon Dots with a Wide Color Gamut and Narrowed Emission Peak Widths.

Carbon dots (CDs) have tremendous potential applications in bioimaging, biomedicine, and optoelectronics. By far, it is still difficult to produce photoluminescence (PL) tunable CDs with high quantum yield (QY) across the entire visible spectrum and narrow the emission peak widths of CDs close to those of typical quantum dots. In this work, a series of CDs with tunable emission from 443 to 745 nm, quantum yield within 13-54%, and narrowed full width at half maximum (FWHM) from 108 to 55 nm, are obtained by only adjusting the reaction solvents in a one-pot solvothermal route. The distinct optical features of these CDs are based on their differences in the particle size, and the content of graphitic nitrogen and oxygen-containing functional groups, which can be modulated by controlling the dehydration and carbonization processes during solvothermal reactions. Blue, green, yellow, red, and even pure white light emitting films (Commission Internationale de L'Eclairage (CIE)= 0.33, 0.33, QY = 39%) are prepared by dispersing one or three kinds of CDs into polyvinyl alcohol with appropriate ratios. The near-infrared emissive CDs are excellent fluorescent probes for both in vitro and in vivo bioimaging because of their high QY in water, long-term stability, and low cytotoxicity.

Four 3D coordination polymers based on layers with single syn-anti carboxylate bridges: synthesis, structures, and magnetic properties.

Four novel coordination polymers (CPs) based on a new 4-(3,5-dicarboxylphenyl) picolinic acid ligands (H3L), [M3(L)2(H2O)6]·4H2O (M3 = Mn3, 1; Co3, 2; Ni3, 3, Co1.01Ni1.99, 4), have been hydrothermally synthesized, and structurally and magnetically characterized. In these isomorphous CPs, octahedrally coordinated metal ions are linked by the single syn-anti carboxylate bridge (µ-COO) to give linear trinuclear motifs. The motifs are connected through the other single syn-anti carboxylate bridge (µ-COO) to give a 2D (4,4) layer, and the layers are interlinked by the L ligands into 3D frameworks. Magnetic measurement indicates that antiferromagnetic interactions between metal ions are mediated through the single syn-anti carboxylate bridges in 1 and 2, while the same carboxylate bridges in 3 transmit ferromagnetic couplings. The bimetallic CP 4 shows interesting complicated magnetic behaviors due to the competition effect of Co(ii) and Ni(ii) ions.

2D carboxylate-bridged LnIII coordination polymers: displaying slow magnetic relaxation and luminescence properties in the detection of Fe3+, Cr2O72- and nitrobenzene.

Eight new 2D isostructural lanthanide coordination polymers (Ln-CPs), [Ln(HL)(H2O)2(NO3)]·NO3 (1-Ln), Ln = NdIII, SmIII, EuIII, GdIII, TbIII, DyIII, HoIII, and YbIII ions, H2L = 4-(3,5-dicarboxylphenyl)-2-methylpyridine, were synthesized by using solvothermal methods and studied by structural analyses, magnetic analyses and luminescent probes. Crystallographic studies revealed that these compounds are 2D frameworks in which dinuclear units with double µ-syn,syn-carboxylate bridges are interlinked by single µ-trans,trans-carboxylate bridges from organic spacers. The layers are further stabilized and combined into 3D architectures through intra- and interlayer ππ stacking interactions and hydrogen bonding, respectively. Magnetic investigations indicated that the carboxylate bridges transmit intralayer antiferromagnetic coupling in 1-Nd, 1-Gd and 1-Ho but transmit intralayer ferromagnetic coupling in 1-Dy. Furthermore, 1-Dy also displays slow magnetic relaxation behavior with a high relaxation energy barrier (ΔUeff) of 100.7 K and a pre-exponential factor (τ0) of 1.4 × 10-8 s under zero dc field. The luminescence investigations showed that CPs 1-Eu and 1-Tb can serve as highly selective and recyclable sensing materials for Fe3+, Cr2O72- and nitrobenzene. Thus, both 1-Eu and 1-Tb should be excellent candidates for multifunctional sensors.

Highly Efficient Red-Emitting Carbon Dots with Gram-Scale Yield for Bioimaging.

Carbon dots (CDs) are a new class of photoluminescent (PL), biocompatible, environment-friendly, and low-cost carbon nanomaterials. Synthesis of highly efficient red-emitting carbon dots (R-CDs) on a gram scale is a great challenge at present, which heavily restricts the wide applications of CDs in the bioimaging field. Herein, R-CDs with a high quantum yield (QY) of 53% are produced on a gram scale by heating a formamide solution of citric acid and ethylenediamine. The as-prepared R-CDs have an average size of 4.1 nm and a nitrogen content of about 30%, with an excitation-independent emission at 627 nm. After detailed characterizations, such strong red fluorescence is ascribed to the contribution from the nitrogen- and oxygen-related surface states and the nitrogen-derived structures in the R-CD cores. Our R-CDs show good photostability and low cytotoxicity, and thus they are excellent red fluorescence probes for bioimaging both in vitro and in vivo.

Facile synthesis of red-emitting carbon dots from pulp-free lemon juice for bioimaging.

In this work, red-emitting carbon dots (R-CDs) with a high quantum yield (QY) of 28% in water were synthesized for the first time by heating an ethanol solution of pulp-free lemon juice. The obtained R-CDs were mono-dispersed with an average diameter of 4.6 nm, and exhibited excitation-independent emission at 631 nm. Meanwhile, these R-CDs featured low cytotoxicity and good photostability, which allow R-CDs to be employed as luminescent probes for in vitro/in vivo bioimaging. In addition, a detailed study on the physical properties and structural compositions of the sodium borohydride (NaBH4) reduced R-CDs with orange emission suggested that surface states on the R-CD surfaces and nitrogen-derived structures in the R-CD cores synergistically caused their intense red luminescence. The low-cost and eco-friendly synthesis method and favorable optical properties of R-CDs make these carbon dots promising for further applications, such as bioimaging and light-emitting diodes.

Synthesis and characterization of polyion complex micelles and their controlled release of folic acid.

Stable and narrow distribution polyion complex micelles (PICMs) were prepared in an aqueous milieu through electrostatic interaction between a pair of oppositely charged block copolymers poly(N-vinylpyrrolidone)-block-poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PVP-b-PAMPS) and monomethoxy poly(ethylene glycol)-block-poly(4-vinyl pyridine) (PEG-b-P4VP). The critical aggregate concentration (CAC), hydrodynamic size, and surface morphology of the prepared PICMs were characterized by fluorescence spectroscopy, dynamic light scattering (DLS), and transmission electron microscopy (TEM), respectively. The resulting CAC and the average diameter of the PICMs were about 43 mg/L and 121 nm, indicating high structural stability of micelles and a size favorable for delivery of drug. In addition, the PICMs exhibited good biocompatibility using the MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide) assay with human embryonic kidney (HEK293) cells. All of these features are quite feasible for utilizing the PICMs as a novel intelligent drug delivery system. In order to assess its application in the biomedical area, the model drug folic acid (FA) was loaded into the micelles and the in vitro drug release behavior was investigated. We found that by manipulating the pH value and salt concentration of the release solution, it was possible to control the release rate of FA.

[Periodic and fractal precipitation in ATP-Co(2+)-decoxycholate gel system].

In the simulation experiments in vitro of the formation of gallstone, adenosine-triphosphate(ATP)-Co(2+)-deoxycholic acid(DC) gel system was chosen to study the periodic precipitation progress. The effect of ATP on the Co(2+)-DC gel system was also determined, and the structure of the periodic precipitation formed was characterized by FTIR. The results show that the patterns formed in the systems with ATP are different, ATP affected the rate and structure of precipitation through its variable participation in the metal coordination complexes as judged by the phosphate P=O bands and the deoxycholate COO- symmetric and asymmetric vibration bands as measured by FTIR Theses spectroscopic differences were correlated with color and pattern differences in the precipitates. ATP has a more remarkable function than AMP to the modes of patterns, meanwhile the system patterns transform from fractal to periodic precipitation. There is a complex interaction among ATP, sodium deoxycholic and Co2+ with a transparent crystal produced. The crystal is deoxycholic acid and the periodic precipitation is composed of ATP and DC covalent to Co2+. These results indicate that stone formation and remodeling is a dynamic, nonlinear progress. Much of the precipitate, as judged by local differences in composition, is not in equilibrium with the general gel environment. The authors conclude that the formation of gallstone features complex and nonlinear chemical character, in which nucleotides as living material play a very important role.

Preparation and properties of a pH/temperature-responsive carboxymethyl chitosan/poly(N-isopropylacrylamide)semi-IPN hydrogel for oral delivery of drugs.

Thermo- and pH-responsive semi-IPN polyampholyte hydrogels were prepared by using carboxymethylchitosan and poly(N-isopropylacrylamide) with N,N'-methylenebisacrylamide (BIS) as the crosslinking agent. The swelling characteristics of these hydrogels at distinct compositions as a function of pH and temperature were investigated. It was found that the semi-IPN hydrogels demonstrated the pH- and temperature-responsive nature of the materials, and it also showed good reversibility. The study on the release of coenzyme A (CoA) showed that within 24h the cumulative release ratio of CoA was 22.6% in pH 2.1 solution and 89.1% in pH 7.4 solution at 37 degrees C, respectively. The release rate of CoA was higher at 37 degrees C than 25 degrees C in a pH 7.4 buffer solution. An increased release rate of CoA was observed with the content of carboxymethylchitosan increasing in the hydrogel at 25 degrees C in pH 7.4 solution. These results show that semi-IPN hydrogel seems to be of great promise in pH-temperature oral drug delivery systems.

[Study on the structure of periodic and chaotic patterns of AMP-DC-Cu-gel systems].

This is an in vitro model to mimic the conditions present during gallstone formation. Adenosine mono-phosphate (AMP), an important bio-molecule, was chosen. Its effect on the formation of periodic/chaotic patterns in the deoxycholate-CuCl2-gel and deoxycholate-CuCl2-glucose-gel systems were studied. FTIR spectroscopy was used to identify the structure of the precipitates. The results indicate that the patterns formed in the systems with AMP are different. And FTIR spectra show that AMP may also be involved in the coordination sphere of Cu2+ ion. The results are more complicated in the deoxycholate-CuCl2 system containing glucose, suggesting that the nonlinear scientific concept should be considered in understanding gallstone formation.