蓝绿光上转换荧光输出的稀土掺杂玻璃研究进展

上转换光纤激光器由于在医疗、生命科学等领域应用逐步加强,近年来受到了广泛的重视.本文简要回顾了上转换发光的发展历程,归纳了能够实现蓝绿光输出的稀土离子的种类,详细阐述了近年来具有蓝绿光输出的上转换发光的不同基质玻璃(氟化物玻璃、硫化物玻璃、碲酸盐玻璃、锗酸盐玻璃、铋酸盐玻璃、卤氧化物玻璃)的研究进展,最后,对稀土离子掺杂的玻璃上转换发光的研究动向进行了展望.     

Endoglin/CD105-Based Imaging of Cancer and Cardiovascular Diseases: A Systematic Review

Molecular imaging of pathologic lesions can improve efficient detection of cancer and cardiovascular diseases. A shared pathophysiological feature is angiogenesis, the formation of new blood vessels. Endoglin (CD105) is a coreceptor for ligands of the Transforming Growth Factor-β (TGF-β) family and is highly expressed on angiogenic endothelial cells. Therefore, endoglin-based imaging has been explored to visualize lesions of the aforementioned diseases. This systematic review highlights the progress in endoglin-based imaging of cancer, atherosclerosis, myocardial infarction, and aortic aneurysm, focusing on positron emission tomography (PET), single-photon emission computed tomography (SPECT), magnetic resonance imaging (MRI), near-infrared fluorescence (NIRF) imaging, and ultrasound imaging. PubMed was searched combining the following subjects and their respective synonyms or relevant subterms: “Endoglin”, “Imaging/Image-guided surgery”. In total, 59 papers were found eligible to be included: 58 reporting about preclinical animal or in vitro models and one ex vivo study in human organs. In addition to exact data extraction of imaging modality type, tumor or cardiovascular disease model, and tracer (class), outcomes were described via a narrative synthesis. Collectively, the data identify endoglin as a suitable target for intraoperative and diagnostic imaging of the neovasculature in tumors, whereas for cardiovascular diseases, the evidence remains scarce but promising.     

上转换材料的制备及发展

上转换材料能将人眼看不见的红外光转变为可见光。这一特性使得上转换材料的研究日益增多,在激光技术、光纤通讯技术、生物分子标记、光信息存储和显示等领域都已经有所应用。文章对上转换材料的发展状况、种类及制备进行了介绍。     

Lanthanide ion-doped GdPO4 nanorods with dual-modal bio-optical and magnetic resonance imaging properties

Here, dual-modal bioprobes for combined optical and magnetic resonance (MR) imaging are reported. Gadolinium orthophosphate (GdPO(4)) nanorods co-doped with light-emitting lanthanide ions have been successfully prepared through a hydrothermal method. An efficient downconversion luminescence from Ce/Tb or Eu doped GdPO(4) nanorods and upconversion luminescence from Yb/Er co-doped GdPO(4) nanorods are observed, respectively, which offers the optical modality for the nanoprobes. Notably, we first report the upconversion phenomenon based on the GdPO(4) matrix under 980 nm near infrared irradiation. The possibility of using these nanoprobes with downconversion and upconversion luminescent emissions for optical cell imaging is also demonstrated. Furthermore, these Gd(3+)-containing nanophosphors show good positive signal-enhancement ability when performed under a 4.7 T MR imaging scanner, indicating they have potential as T(1) MR imaging contrast agents. Thus, nanoprobes based on GdPO(4) nanophosphors are shown to provide the dual modality of optical and MR imaging.     

A DNA sensor based on upconversion nanoparticles and two-dimensional dichalcogenide materials

We demonstrate the fabrication of a new DNA sensor that is based on the optical interactions occurring between oligonucleotide-coated NaYF₄: Yb³⁺; Er³⁺ upconversion nanoparticles and the two-dimensional dichalcogenide materials, MoS₂ and WS₂. Monodisperse upconversion nanoparticles were functionalized with single-stranded DNA endowing the nanoparticles with the ability to interact with the surface of the two-dimensional materials via van der Waals interactions leading to subsequent quenching of the upconversion fluorescence. By contrast, in the presence of a complementary oligonucleotide target and the formation of double-stranded DNA, the upconversion nanoparticles could not interact with MoS₂ and WS₂, thus retaining their inherent fluorescence properties. Utilizing this sensor we were able to detect target oligonucleotides with high sensitivity and specificity whilst reaching a concentration detection limit as low as 5 mol·L^–1, within minutes.     

Functioning nanomachines seen in real-time in living bacteria using single-molecule and super-resolution fluorescence imaging

Molecular machines are examples of "pre-established" nanotechnology, driving the basic biochemistry of living cells. They encompass an enormous range of function, including fuel generation for chemical processes, transport of molecular components within the cell, cellular mobility, signal transduction and the replication of the genetic code, amongst many others. Much of our understanding of such nanometer length scale machines has come from in vitro studies performed in isolated, artificial conditions. Researchers are now tackling the challenges of studying nanomachines in their native environments. In this review, we outline recent in vivo investigations on nanomachines in model bacterial systems using state-of-the-art genetics technology combined with cutting-edge single-molecule and super-resolution fluorescence microscopy. We conclude that single-molecule and super-resolution fluorescence imaging provide powerful tools for the biochemical, structural and functional characterization of biological nanomachines. The integrative spatial, temporal, and single-molecule data obtained simultaneously from fluorescence imaging open an avenue for systems-level single-molecule cellular biophysics and in vivo biochemistry.     

Spectrofluorometric and Molecular Docking Studies on the Binding of Curcumenol and Curcumenone to Human Serum Albumin

Curcumenol and curcumenone are two major constituents of the plants of medicinally important genus of Curcuma, and often govern the pharmacological effect of these plant extracts. These two compounds, isolated from C. zedoaria rhizomes were studied for their binding to human serum albumin (HSA) using the fluorescence quench titration method. Molecular docking was also performed to get a more detailed insight into their interaction with HSA at the binding site. Additions of these sesquiterpenes to HSA produced significant fluorescence quenching and blue shifts in the emission spectra of HSA. Analysis of the fluorescence data pointed toward moderate binding affinity between the ligands and HSA, with curcumenone showing a relatively higher binding constant (2.46 × 10⁵ M⁻¹) in comparison to curcumenol (1.97 × 10⁴ M⁻¹). Cluster analyses revealed that site I is the preferred binding site for both molecules with a minimum binding energy of −6.77 kcal·mol⁻¹. However, binding of these two molecules to site II cannot be ruled out as the binding energies were found to be −5.72 and −5.74 kcal·mol⁻¹ for curcumenol and curcumenone, respectively. The interactions of both ligands with HSA involved hydrophobic interactions as well as hydrogen bonding.     

Multicolored nanometre-resolution mapping of single protein-ligand binding complexes using far-field photostable optical nanoscopy (PHOTON)

Mapping of individual ligand molecules and their binding sites in single protein-ligand complexes at nanometer resolution in real-time would enable probing their structures and functions in vitro and in vivo. In this study, we have developed far-field photostable optical nanoscopy (PHOTON) for mapping single ligand molecules (biotin) and their binding sites in individual protein-ligand complexes (streptavidin-biotin) with 1.2 nm spatial resolution and 100 ms temporal resolution. PHOTON includes one standard far-field optical microscope with a halogen-lamp illuminator; single-molecule-nanoparticle-optical-biosensors (SMNOBS) with exceptionally high quantum-yield (QY) of Rayleigh scattering and photostability (non-photobleaching, non-photoblinking) as imaging probes; and Multispectral Imaging System (MSIS) for spectral isolation of individual SMNOBS with 1 nm wavelength resolution. Intrinsic size- and shape- dependent localized-surface-plasmon-resonance (LSPR) spectra of single SMNOBS provide multiple-spectral (color) nanoprobes for sub-diffraction imaging, offering feasibility of probing of binding structures and functions of single protein-ligand complexes at nm (potentially achieving ?ngstrom) resolution in real-time.     

Highly Efficient Near-IR Photoluminescence of Er Immobilized in Mesoporous SBA-15

SiO₂ mesoporous molecular sieve SBA-15 with the incorporation of erbium ions is studied as a novel type of nanoscopic composite photoluminescent material in this paper. To enhance the photoluminescence efficiency, two schemes have been used for the incorporation of Er³⁺ where (1) Er³⁺ is ligated with bis-(perfluoromethylsulfonyl)-aminate (PMS) forming Er(PMS)_x-SBA-15 and (2) Yb³⁺ is codoped with Er³⁺ forming Yb-Er-SBA-15. As high as 11.17 × 10⁻²¹cm² of fluorescent cross section at 1534 nm and 88 nm of “effective bandwidth” have been gained. It is a 29.3% boost in fluorescent cross section compared to what has been obtained in conventional silica. The upconversion coefficient in Yb-Er-SBA-15 is relatively small compared to that in other ordinary glass hosts. The increased fluorescent cross section and lowered upconversion coefficient could benefit for the high-gain optical amplifier. Finally, the Judd–Ofelt theory has also been used for the analyses of the optical spectra of Er(PMS)_x-SBA-15.     

New Peptide-Conjugated Chlorin-Type Photosensitizer Targeting Neuropilin-1 for Anti-Vascular Targeted Photodynamic Therapy

Photodynamic therapy (PDT) is a cancer treatment modality that requires three components, namely light, dioxygen and a photosensitizing agent. After light excitation, the photosensitizer (PS) in its excited state transfers its energy to oxygen, which leads to photooxidation reactions. In order to improve the selectivity of the treatment, research has focused on the design of PS covalently attached to a tumor-targeting moiety. In this paper, we describe the synthesis and the physico-chemical and photophysical properties of six new peptide-conjugated photosensitizers designed for targeting the neuropilin-1 (NRP-1) receptor. We chose a TPC (5-(4-carboxyphenyl)-10,15, 20-triphenyl chlorine as photosensitizer, coupled via three different spacers (aminohexanoic acid, 1-amino-3,6-dioxaoctanoic acid, and 1-amino-9-aza-3,6,12,15-tetraoxa-10-on-heptadecanoic acid) to two different peptides (DKPPR and TKPRR). The affinity towards the NRP-1 receptor of the conjugated chlorins was evaluated along with in vitro and in vivo stability levels. The tissue concentration of the TPC-conjugates in animal model shows good distribution, especially for the DKPPR conjugates. The novel peptide–PS conjugates proposed in this study were proven to have potential to be further developed as future NRP-1 targeting photodynamic therapy agent.     

上转换/半导体核壳结构纳米复合材料光催化研究进展

上转换荧光材料具有将近红外光转换为紫外光和可见光的光学性能,与传统的半导体材料复合,使其光谱响应拓展到近红外区域,充分利用太阳光,从而提高光催化效率。核壳结构除能够有效地防止核(上转换纳米材料)被污染失活外,还可以使其紧密接触,有利于荧光共振能量的传递,提高壳(半导体材料)对光的利用率。系统论述了上转换半导体核壳结构纳米复合材料的制备方法、催化降解效率和催化影响因素,对此类复合材料的结合和催化机理进行分析,指出今后应加强高效率荧光材料和催化活性更强的半导体材料复合及如何在实际中应用的研究。     

A study of photoluminescence properties and performance improvement of Cd-doped ZnO quantum dots prepared by the sol-gel method

ABSTRACT: In the present work, ZnO quantum dots (QDs) have been prepared by the sol-gel method, and the performance of the QDs have been improved. The effect of Cd concentration on the structural and luminescent properties of the QDs, as well as the effect of the mass ratio of trioctylphosphine oxide (TOPO)/octadecylamine (ODA), has been investigated. The ZnO and Cd-doped ZnO QDs have hexagonal wurtzite structures and are 3~6 nm in diameter. When the Cd content was increased, the QD particle size was reduced; this effect was confirmed in the corresponding ultraviolet-visible (UV) spectra. The fluorescence intensity was simultaneously enhanced significantly. Both the UV and fluorescence spectra were blue-shifted. The luminous intensity was further enhanced when the QDs were modified with TOPO/ODA. FTIR and XRD techniques proved that the polymer successfully coated the surfaces of the QDs. A TOPO/ODA mass ratio of 1:2 was determined to result in the best optical performance among the different ratios examined. The results showed that the described synthetic method is appropriate for the preparation of doped QDs with a high fluorescence quantum efficiency.     

Development of biocompatible NaGdF4: Er3+, Yb3+ upconversion nanoparticles used as contrast agents for bio‐imaging

Upconversion nanoparticles with special fluorescence and magnetic properties have been considered an alternative contrast agent for multiple bio‐imaging techniques. It is important to understand the effects of the surface properties and dosage of upconversion nanoparticles on both the magnetic resonance (MRI) image and the photoluminescence spectrum. Here, NaGdF₄: Er³⁺, Yb³⁺ upconversion nanoparticles (UCNPs) modified with amine functional group were produced through a one‐pot thermal decomposition. The average length of the cubic UCNPs is estimated at 53 ±13 nm. The effect of the dosage of amine modified UCNPs on the MRI image is investigated. The T₁ and T₂ relaxivities of the amine modified UCNPs in agarose gel at 3 T are r₁ = 6.79 ±0.14 and r₂ = 17.0 ±0.18 (mmol/L)^?1 s^?1, which are comparable to the relaxivities of commercially available MRI contrast agents. In addition, the photoluminescence of the amine modified UCNPs at low concentrations < 150 µg/mL are further investigated with the excitation wavelength (λ_ex) at 980 nm. The internalization of the amine modified UCNPs cultured with human umbilical vascular endothelial cells (HUVEC) is observed by the fluorescence imaging. Meanwhile, T₁‐weighted MRI imaging of HUVEC cells treated with amine modified UCNPs at 10 µg/mL can be obtained. No significant toxic effect on cells is found when the concentration of the amine modified UCNPs is < 300 µg/mL. This study indicates that a low concentration of amine‐modified NaGdF₄: Er³⁺, Yb³⁺ UCNPs can be used as the contrast agent for both fluorescence imaging and magnetic resonance imaging.     

Germanate-based oxyfluoride transparent glass-ceramic embedded with Tm3+:Ca2YbF7 nanocrystals for high-performance optical thermometer

Germanate-based oxyfluoride transparent glass-ceramic functionalized by Tm³⁺:Ca₂YbF₇ nanocrystals was newly developed. The tremendously enhanced upconversion emission of ³F_2,3 energy levels by in situ crystallization was extremely beneficial for constructing optical thermometry involving the indirect thermally coupled energy levels (¹G₄ and ³F_2,3) of Tm³⁺ ions. Utilizing the fluorescence intensity ratio technique, the thermometry potentials of PG and GC8 were systematically evaluated based on the emissions from ³F_2,3 and ¹G₄ energy levels. The relative and absolute sensitivities, thermometry resolutions, and repeatabilities were superior to many reported materials. This work provides an avenue for precipitating ternary fluoride nanocrystals containing rare earths in germanate-based oxyfluoride glass, and proposes a promising way to achieve high performance optical thermometry based on the emissions from widely spaced energy levels.     

Luminogenic polymers with aggregation-induced emission characteristics

Aggregation-induced emission (AIE) is a newly developed phenomenon that is exactly opposite to the aggregation-caused emission quenching effect observed with some conventional luminophores. The AIE phenomenon was first realized in propeller-like small molecules and now has extended to polymeric systems. In this review, we summarize the recent progress on the preparation of luminogenic polymers with AIE or aggregation-enhanced emission (AEE) characteristics, which are generally prepared by attaching AIE-active luminogens, such as tetraphenylethene and silole, as pendants to the polymer backbones or utilizing them as skeletons for main chain polymers. An AIE phenomenon was observed in succinic anhydride-containing nonconjugated polymers bearing no luminogens, presumably due to the agglomeration of carbonyl groups. The AIE/AEE-active polymers show unique properties, such as emission superquenching, high and tunable light refractivity, and aggregation-enhanced two-photon excited fluorescence, and have found potential applications as fluorescent sensors, biological probes, and active layers for the fabrication of light-emitting diodes.     

Altered DNA Binding and Amplification of Human Breast Cancer Suppressor Gene BRCA1 Induced by a Novel Antitumor Compound, [Ru(��6-p-phenylethacrynate)Cl2(pta)]

The ruthenium-based complex [Ru(η⁶-p-phenylethacrynate)Cl₂(pta)] (pta = 1,3,5-triaza-7-phosphatricyclo-[3.3.1.1]decane), termed ethaRAPTA, is an interesting antitumor compound. The elucidation of the molecular mechanism of drug activity is central to the drug development program. To this end, we have characterized the ethaRAPTA interaction with DNA, including probing the sequence specific modified DNA structural stability and DNA amplification using the breast cancer suppressor gene 1 (BRCA1) of human breast and colon adenocarcinoma cell lines as models. The preference of ethaRAPTA base binding is in the order A > G > T > C. Once modified, the ethaRAPTA-induced BRCA1 structure has higher thermal stability than the modified equivalents of its related compound, RAPTA-C. EthaRAPTA exhibits a higher efficiency than RAPTA-C in inhibiting BRCA1 amplification. With respect to both compounds, the inhibition of BRCA1 amplification is more effective in an isolated system than in cell lines. These data provide evidence that will help to understand the process of elucidating the pathways involved in the response induced by ethaRAPTA.     

镧系掺杂上转换发光纳米材料的研究进展

上转换发光纳米材料在生物分析和医学成像中具有优异的应用前景。对上转换过程的研究正迅速发展为光化学、生物物理学、固体物理学和材料学的交叉领域。与有机荧光染料和量子点相比,镧系掺杂纳米晶体在生物荧光标记方面具有更少的限制条件。概述了镧系掺杂纳米晶体的结构和上转换发光机理,综述了镧系掺杂上转换发光纳米材料的合成、发光颜色调控方法及其生物分析应用方面的研究进展。     

Antiangiogenesis,Loss of Cell Adhesion and Apoptosis Are Involved in the Antitumoral Activity of Proteases from V. cundinamarcensis (C. candamarcensis) in Murine Melanoma B16F1

The proteolytic enzymes from V. cundinamarcensis latex, (P1G10), display healing activity in animal models following various types of lesions. P1G10 or the purified isoforms act as mitogens on fibroblast and epithelial cells by stimulating angiogenesis and wound healing in gastric and cutaneous ulcers models. Based on evidence that plant proteinases act as antitumorals, we verified this effect on a murine melanoma model. The antitumoral effect analyzed mice survival and tumor development after subcutaneous administration of P1G10 into C57BL/6J mice bearing B16F1 low metastatic melanoma. Possible factors involved in the antitumoral action were assessed, i.e., cytotoxicity, cell adhesion and apoptosis in vitro, haemoglobin (Hb), vascular endothelial growth factor (VEGF), tumor growth factor-β (TGF-β), tumor necrosis factor-α (TNF-α) content and N-acetyl-glucosaminidase (NAG) activity. We observed that P1G10 inhibited angiogenesis measured by the decline of Hb and VEGF within the tumor, and TGF-β displayed a non-significant increase and TNF-α showed a minor non-significant reduction. On the other hand, there was an increase in NAG activity. In treated B16F1 cells, apoptosis was induced along with decreased cell binding to extracellular matrix components (ECM) and anchorage, without impairing viability.     

Yb/Er/Ho-α-SiAlON ceramics for high-temperature optical thermometry

Maximum operating temperature in optical thermometry is limited due to poor thermal stability of the sensing material at high temperatures. Here, Yb, Er and Ho-doped α-SiAlON (Yb/Er/Ho-α-SiAlON) ceramic prepared by hot press method has been studied for optical thermometry via upconversion under 980 nm excitation. The phase of the sintered ceramic has been confirmed by Rietveld refinement of the X-ray diffraction data. The temperature-dependent upconversion was studied in a wide temperature range of 298–1023 K and fluorescence intensity ratio technique was used for temperature sensing behavior. Excellent spectral/thermal stability over the investigated temperature range was observed for the Yb/Er/Ho-α-SiAlON as the sensing material. The maximum values of absolute and relative sensitivity based on the thermally coupled levels of Er³⁺ are 59.2 × 10^?4 K^?1 and 1.10 %.K^?1 at 298 K and that based on non-thermally coupled levels are 108 × 10^?4 K^?1 at 385 K and 0.345 %.K^?1 at 329 K, respectively.