Hybrid metal halide family with color-time-dual-resolved phosphorescence for multiplexed information security applications.

Luminescent materials with engineered optical properties play an important role in anti-counterfeiting and information security technology. However, conventional luminescent coding is limited by fluorescence color or intensity, and high-level multi-dimensional luminescent encryption technology remains a critically challenging goal in different scenarios. To improve the encoding capacity, we present an optical multiplexing concept by synchronously manipulating the emission color and decay lifetimes of room-temperature phosphorescence materials at molecular level. Herein, we devise a family of zero-dimensional (0D) hybrid metal halides by combining organic phosphonium cations and metal halide tetrahedral anions as independent luminescent centers, which display blue phosphorescence and green persistent afterglow with the highest quantum yields of 39.9 % and 57.3 %, respectively. Significantly, the luminescence lifetime can be fine-tuned in the range of 0.0968-0.5046 µs and 33.46-125.61 ms as temporary time coding through precisely controlling the heavy atomic effect and inter-molecular interactions. As a consequence, synchronous blue phosphorescence and green afterglow are integrated into one 0D halide platform with adjustable emission lifetime acting as color- and time-resolved dual RTP materials, which realize the multiple applications in high-level anti-counterfeiting and information storage. The color-lifetime-dual-resolved encoding ability greatly broadens the scope of luminescent halide materials for optical multiplexing applications.

Multifunctional Crystalline Coordination Polymers Constructed from 4,4'-Bipyridine-N,N'-dioxide: Photochromism, White-Light Emission, and Photomagnetism.

Multifunctional photochromic coordination polymers (CPs) have shown great potential in many areas, like molecular switches, anticounterfeiting, magnetics, and optoelectronics. Although multifunctional photochromic CPs can be obtained by introducing photoresponsive functional units or by exploiting the synergy effect of each component, relatively limited photochromic ligands hinder the development of various multifunctional photochromic CPs. In this work, we reported two multifunctional coordination polymers {[Zn(bpdo)(fum)(H2O)2]}n (1) and {[Mn(bpdo)(fum)(H2O)2]}n (2) based on an easily accessible but underestimated photoactive molecule 4,4'-bipyridine-N,N'-dioxide (bpdo). Compound 1 exhibits photochromism and white-light emission with an ultra-high color rendering index (CRI) of 92.1. Interestingly, compound 1 could emit intrinsic white light in the crystalline state upon UV irradiation both before and after photochromism. Meanwhile, compound 2 displays photochromic and photomagnetic properties, induced by the photogenerated radicals via a photoinduced electron transfer mechanism.

2,4,6-Tri(4-pyridyl)-1,3,5-triazine: Photoinduced Charge Separation and Photochromism in the Crystalline State.

2,4,6-Tri(4-pyridyl)-1,3,5-triazine (tpt) is a widely used ligand for functional coordination compounds. In this work, tpt has shown unprecedented photochromism in the crystalline state. Experimental and theoretical data has revealed that the photocoloration of tpt very likely originates from intramolecular charge separation and the formation of a triplet diradical product. This finding demonstrates a new simple, neutral photochromic molecule and endows the tpt molecule and related compounds with potential optical applications.

[Expression and Clinical Significance of Leukemia Stem Cell Antigen in Acute Myeloid Leukemia].

OBJECTIVE: To analyze the expression characteristics of leukemia stem cell (LSC) antigen in acute myeloid leukemia (AML) and to explore the correation of LSC-specific antigens with the subtypes, cytogenetics and clinical efficacy of AML. METHODS: A total of 61 newly diagnosed patients with AML (except M3) hospltalized in Department of Hematology of our hopital were selected from January 2013 to March 2016. The immun phenotypes and expression of Tim-3, CD96 and CD123 on leucamia cells were detected by direct immunofluorescenct flow cytometry. 61 patients were divided into positive expression and megative expression groups according to expression of Tim-3, CD96 and CD123; the correlation of LSC antigen expression level with high WBC count, chromosome and therapeutic efficacy was analyzed. RESULTS: Among 61 newly diagnosed patients with AML (except M3), the expression rate of Tim-3, CD96 and CD123 was 52.45%, 44.26% and 55.73% respectively. The expression rates of Tim-3, CD96 and CD123 between the AML subtypes and total patients was not stetistically different (P>0.05). The high WBC count occurred more easily in AML (except MS) patients with positive expression of Tim-3, CD96 and CD123, but compared with AML patients with negative espression, the difference was not statstically significant (P>0.05). The proportion of chromosone karyotype with poor prognosis detected in patients with positive expression of Tim-3 and CD96 was higher than that in patients with negative expreesion (P<0.05); while the preoprtion of chromosome karyotype with poor prognosis detected in patients with positive and negative expression of CD123 was not significantly different (P>0.05). After 2 courses of chemotherapy, the complete remission (CR) rate in patients with positive expression of Tim-3, CD96 and CD123 was significantly lower than that in patients with negative expression of Tim-3, CD96 and CD123 (P<0.05), the comparison of OS time in patients with positive and negative expression of Tim-3 and CD96 showed the statistical difference (P>0.05), while the difference of OS time in patients with positive and negative expression of CD123 was not significant (P>0.05). CONCLUSION: The expression levels of Tim-3, CD96 and CD123 in newly diagnosed AML (except M3) sybtype patients are not significantly different form those in total patients. The high WBC count ocours more easily in patients with positive expression of Tim-3, CD96 and CD123. After 2 course of chemotherapy, the CR rate in patients with positive expression of Tim-3, CD96 and CD123 was significantly lower than that in patients with negative expression. The proportion of chromsome karyotype with poor prognosis detected in patients with positive expression of Tim-3 and CD96 is high, moreover, OS time in patients with positive expression of Tim-3 and CD96 is shorter than that in patients with negative expression.

Transition-Metal-Complex Cationic Dyes Photosensitive to Two Types of 2D Layered Silver Bromides with Visible-Light-Driven Photocatalytic Properties.

With mixed transition-metal (TM) complex, alkali-metal cations, or halogen anions as structure-directing agents, two types of two-dimensional (2D) layered inorganic-organic hybrid silver bromides were prepared and structurally characterized as K[TM(2,2-bipy)3]2Ag6Br11 (TM = Ni (1), Co (2), Zn (3), Fe (4)) and [TM(2,2-bipy)3]2Ag13Br17 (TM = Ni (5), Co (6), Zn (7), Fe (8)). Compounds 1-4 feature 2D microporous anionic [Ag6Br11]5- layers composed of [Ag3Br7] secondary building units based on AgBr4 tetrahedral units, and compounds 5-8 contain 2D [Ag13Br16]3- layers built from the one-dimensional complex [Ag8Br12] and [Ag5Br8] chains. The photosensitization of TM complex dyes led to the narrow semiconducting behaviors with tunable band gaps of 1.73-2.71 eV for the title compounds, which result in excellent and stable photocatalytic degradation activities over organic pollutants under visible-light irradiation. The studies of photocatalytic mechanism based on radical-trapping experiments and electronic band structural calculation show that the TM complex cations play important roles in the photocatalytical activities and photochemical stabilities due to their excellent separating abilities for photogenerated carriers. This technique affords one new type of visible-light-driven photocatalyst and facilitates the integration of 2D layered materials and semiconducting photocatalytic properties into one hybrid d10 TM halogenide.

Two Types of 2D Layered Iodoargentates Based on Trimeric [Ag3I7] Secondary Building Units and Hexameric [Ag6I12] Ternary Building Units: Syntheses, Crystal Structures, and Efficient Visible Light Responding Photocatalytic Properties.

With mixed transition-metal-complex, alkali-metal, or organic cations as structure-directing agents, a series of novel two-dimensional (2D) layered inorganic-organic hybrid iodoargentates, namely, Kx[TM(2,2-bipy)3]2Ag6I11 (TM = Mn (1), Fe (2), Co (3), Ni (4), Zn (5); x = 0.89-1) and [(Ni(2,2-bipy)3][H-2,2-bipy]Ag3I6 (6), have been solvothermally synthesized and structurally characterized. All the title compounds feature 2D microporous layers composed by [Ag3I7] secondary building units based on AgI4 tetrahedra. Differently, the [Ag3I7] trimers are directly interconnected via corner-sharing to form the 2D [Ag6I11](5-) layer in compounds 1-5, whereas two neighboring [Ag3I7] trimers are initially condensed into a hexameric [Ag6I12] ternary building unit as a new node, which further self-assembles, leading to the 2D [Ag6I10](4-) layer in compound 6. The UV-vis diffuse-reflectance measurements reveal that all the compounds possess proper semiconductor behaviors with tunable band gaps of 1.66-2.75 eV, which lead to highly efficient photocatalytic degradation activities over organic pollutants under visible light irradiation compared to that of N-dotted P25. Interestingly, all the samples feature distinct photodegradative speeds at the same reaction conditions, and compound 1 features the highest photocatalytic activity among the title phases. The luminescence properties, band structures, and thermal stabilities were also studied.