Nanosized Carbon Macrocycles Based on a Planar Chiral Pseudo Meta-[2.2]Paracyclophane

Structural designs combining cycloparaphenylenes (CPPs) backbone with planar chiral [2.2]paracyclophane ([2.2]PCP) lead to optical-active chiral macrocycles with intriguing properties. X-ray crystal analysis revealed aesthetic necklace-shaped structures and size-dependent packages with long-range channels. The macrocycles exhibit unique photophysical properties with high fluorescence quantum yield of up to 82 %, and the fluorescent color varies with ring size. In addition, size-dependent chiroptical properties with moderately large CPL dissymmetry factor of 10⁻³ and CPL brightness in the range of 30–40 M⁻¹ cm⁻¹ were observed.     

Multiply Twisted Chiral Macrocycles Clamped by Tethered Binaphthyls Exhibiting High Circularly Polarized Luminescence Brightness

Chiral macrocyclic dimers, trimers, and tetramers composed of paraphenylene and tethered binaphthyl were synthesized, and their molecular structures and chiroptical properties were investigated. X-ray analysis and theoretical calculations revealed that multiple twisted molecular structures – dimers, trimers, and tetramers – adopt figure-of-eight, Möbius triangle, and concave rectangle structures, respectively. These homologues have large ϵ values in their UV-vis absorption spectra because of the π-conjugation of the naphthalene-phenylene-naphthalene frameworks. Owing to the shape-persistent ring structure and tethering with −OCH₂CH₂O−, high fluorescence quantum yields and a relatively high dissymmetry factor g_CPL in circularly polarized luminescence (CPL) spectra were achieved. This results in CPL brightness (B_CPL) of over 100, which is greater than that of the conventional organic CPL dye.     

Luminescent Graphene-Based Materials via Europium Complexation on Dipyridylpyridazine-Functionalized Graphene Sheets

Graphene-based materials exhibit outstanding physical properties and so are potentially applicable in a great variety of fields. Unlike their corresponding oxides, graphite and graphene are not prone to functionalization. Diels–Alder reactions are among the scarce reactions that they can occur without disrupting their conjugated sp² systems. Herein, the reaction between graphite and 3,6-di(2-pyridyl)-1,2,4,5-tetrazine under different conditions affords several graphene-based materials consisting of dipyridylpyridazine-functionalized few-layer graphene, multilayer graphene and graphite, the sheets of which act as ligands for the grafting of a europium complex. These three materials show strong red emission under 365 nm UV radiation. Their emitting particles can be visualized by confocal microscopy. The rich coordination chemistry of dipyridylpyridazine ligands has potential novel properties for similarly functionalized graphene-based materials grafted with other metal complexes.     

Assembled synthesis of luminescent mono/double‐layered 2D and 3D Zn (II)‐based coordination polymers tuned by flexible bis (pyridyl)propane‐1,2‐diamines and diverse organic dicarboxylates

Six mono/double‐layered 2D and three 3D coordination polymers were synthesized by a self‐assembly reaction of Zn (II) salts, organic dicarboxylic acids and L1/L2 ligands. These polymeric formulas are named as [Zn(L1)(C₄H₂O₄)_0.5 (H₂O)]_n·0.5n(C₄H₂O₄)·2nH₂O ( 1 ), [Zn₂(L2)(C₄H₂O₄)₂]_n·2nH₂O ( 2 ), [Zn(L1)(m‐BDC)]_n ( 3 ), [Zn₂(L2)(m‐BDC)₂]_n·2nH₂O ( 4 ), [Zn₃(L1)₂(p‐BDC)₃(H₂O)₄]_n·2nH₂O ( 5 ), [Zn₂(OH)(L2) (p‐BDC)_1.5]_n ( 6 ), [Zn₂(L1)(p‐BDC)₂]_n·5nH₂O ( 7 ), [Zn₂(L2)(p‐BDC)₂]_n·3nH₂O ( 8 ) and [Zn₂(L1)(C₄H₄O₄)_1.5(H₂O)]_n·n(ClO₄)·nH₂O ( 9 ) [L1 = N,N′‐bis (pyridin‐4‐ylmethyl)propane‐1,2‐diamine, L2 = N,N′‐bis (pyridin‐3‐ylmethyl)propane‐1,2‐ diamine, m‐BDC^2? = m‐benzene dicarboxylate, p‐BDC^2? = p‐benzene dicarboxylate]. Meanwhile, these polymers have been characterized by elemental analysis, infrared, thermogravimetry (TG), photoluminescence, powder and single‐crystal X‐ray diffraction. Polymers 1–6 present mono‐ and double (4,4)‐layer motifs accomplished by L1/L2 ligands with diverse conformations and organic dicarboxylates, and the layer thickness locates in the range of 5.8–15.0 Å. In three 3D polymers, the L1 and L2 molecules adopt the same cis‐conformations and join adjacent Zn (II) cations together with p‐BDC^2? or succinate, giving rise to different binodal (4,4)‐c nets with (4.5².8³)(4.5³.7²) ( 7 ), pts ( 8 ) topology and twofold interpenetrated binodal (5,5)‐c nets with (3².4⁴.5².6²)(3.4³.5².6⁴) ( 9 ). Therefore, the diverse conformations of the two bis (pyridyl)‐propane‐1,2‐diamines and the feature of different organic dicarboxylate can effectively influence the architectures of these polymers. Powder X‐ray diffraction patterns demonstrate that these bulk solid polymers are pure phase. TG analyses indicate that these polymers have certain thermal stability. Luminescent investigation reveals that the emission maximum of these polymers varies from 402 to 449 nm in the solid state at room temperature. Moreover, 1 , 3 and 5–8 show average luminescence lifetimes from 8.81 to 16.30 ns.     

Separation of antipyretic analgesics by open tubular capillary electrochromatography with homopolymer coatings

This study developed an open‐tubular capillary electrochromatography protocol for the analysis of antipyretic analgesic drugs, which used a multifunctional homopolymer as coating. A controlled/living radical polymerization strategy was adopted to obtain poly(N‐acryloxysuccinimide) with a tunable chain‐length. The homopolymer coating enhanced the separation performance by contributing to the hydrophobic and hydrogen‐bonding interactions between the analytes and the homopolymer. The effect of polymer chain‐length and buffer pH and concentration on the separation efficiency was evaluated. In this approach, baseline separation of the three test drugs was achieved within 15 min. The repeatability of the prepared homopolymer coating was investigated, with the relative standard deviations < 2.88% observed in intra‐ and interday runs. Good linearity in the 5–800 µM range (R² ≥ 0.998) demonstrates that accurate quantitative analysis of real samples was achieved. Moreover, the proposed assay was used to quantify the three drugs (aminopyrine, 4‐aminoantipyrine, and phenacetin) in urine samples, achieving recovery rates between 92.1 and 108.7%. This promising methodology may be used for the analysis of drugs in real bio‐samples and for the development of unique homopolymer coatings for open‐tubular capillary electrochromatography systems.     

Simultaneous separation and determination of seven isoflavones in Radix Puerariae by capillary electrophoresis with a dual cyclodextrin system

A simple, comprehensive and efficient capillary electrophoresis method using a dual cyclodextrin system was developed for the simultaneous determination of seven isoflavones (3′‐methoxypuerarin, puerarin, 3′‐hydroxypuerarin, ononin, daidzin, daidzein and genistin). Baseline separations of the seven isoflavones were achieved within 11 min with the running buffer consisting of 35 mm sodium tetraborate, 9.0 mm sulfobutylether‐β‐cyclodextrin and 30 mm α‐cyclodextrin at pH 9.34, and peaks were detected at 254 nm. Other separation parameters included the separation voltage for 15 kV and the working temperature for 25°C. Under the optimum conditions, good linearities were obtained with linear correlation coefficients of seven isoflavones of 0.9978–0.9992. The limits of detection and the limits of quantification were 0.7–2.9 and 2.5–9.5 μg/mL, respectively. Excellent precision and accuracy were obtained. The intraday and interday precision ranged from 0.7 to 2.0% and from 0.8 to 1.9%, respectively. The recoveries of seven analytes were from 97.7 to 103.1%. This method was successfully applied to determine the seven analytes in Radix Puerariae and its preparations.     

Detection of synergistic effect of superoxide dismutase and jujubosides on scavenging superoxide anion radical by capillary electrophoresis

A new capillary electrophoresis method was developed to study the synergistic effect of superoxide dismutase and jujuboside A or B on scavenging superoxide anion radical in serum matrix respectively, in which superoxide anion radical was generated from pyrogallol autoxidation. The electrophoresis conditions, and the factors affecting the productive rate of purpurogallin, such as pyrogallol autoxidation product and the activity of superoxide dismutase, were optimized. Under optimal conditions, the content of superoxide dismutase in Gibco newborn calf serum was 7.06 mg/L, RSD was 2.01% and the average recovery was 98.4%. The values of IC₅₀ for jujuboside A and B in the serum matrix were 157.67 and 31.60 mg/L respectively, and they both had synergy on scavenging superoxide anion radical with superoxide dismutase, but there was no the dose‐dependency on this synergy.     

Er3+单掺、Er3+/Yb3+共掺杂Ca12Al14O32F2的 制备及上转换发光性质

利用高温固相法成功制备了Er~(3+)单掺、Er~(3+)/Yb~(3+)共掺杂Ca_(12)Al_(14)O_(32)F_2上转换发光样品。在980 nm激光激发下,Er~(3+)单掺和Er~(3+)/Yb~(3+)共掺杂样品均呈现出较强的绿光(528,549 nm)和较弱的红光(655 nm)发射,分别归因于Er~(3+)离子的~2H_(11/2),~4S_(3/2)→~4I_(15/2)和~4F_(9/2)→~4I_(15/2)能级跃迁。随着Er离子浓度的增加,单掺杂样品上转换发光强度先增大后减小,最佳掺杂浓度为0.8%。共掺杂Yb~(3+)后,Er~(3+)的发光强度明显增大。还原气氛下合成的样品上转换发光强度增大约两倍,可能和笼中阴离子基团变化有关。发光强度和激发光功率的关系表明所得上转换发射为双光子吸收过程,借助Er~(3+)-Yb~(3+)体系能级结构详细讨论了上转换发射的跃迁机制。     

Strong red emissions induced by Pt–Pt interactions in binuclear cycloplatinated(II) complexes containing bridging diphosphines

A series of dinuclear cycloplatinated(II) complexes with general closed formula of [Pt₂Me₂(C^N)₂(μ‐P^P)] (C^N = 2‐vinylpyridine (Vpy), 2,2′‐bipyridine N‐oxide (O‐bpy), 2‐(2,4‐difluorophenyl)pyridine (dfppy); P^P = 1,1‐bis(diphenylphosphino)methane (dppm), N,N‐bis(diphenylphosphino)amine (dppa)) are reported. The complexes were characterized by means of NMR spectroscopy. Due to the presence of dppm and dppa with short backbones as bridging ligands, two platinum centres are located in front of each other in these complexes so a Pt…Pt interaction is established. Because of this Pt…Pt interaction, the complexes have bright orange colour under ambient light and are able to strongly emit red light under UV light exposure. These strong red emissions originate from a ³MMLCT (metal–metal‐to‐ligand charge transfer) electronic transition. In most of these complexes, the emissions have unstructured bell‐shaped bands, confirming the presence of large amount of ³MMLCT character in the emissive state. Only the complexes bearing dfppy and dppa ligands reveal dual luminescence: a high‐energy structured emission originating from ³ILCT/³MLCT (intra‐ligand charge transfer/metal‐to‐ligand charge transfer) and an unstructured low‐energy band associated with ³MMLCT. In order to describe the nature of the electronic transitions, density functional theory calculations were performed for all the complexes.     

Near-IR Luminescent YbIII Coordination Polymers Composed of Pyrene Derivatives for Thermostable Oxygen Sensors

Oxygen-sensitive and near-infrared (NIR) luminescent Yb^III coordination polymers incorporating ligands based on pyrene derivatives were synthesized: Yb^III–TBAPy and Yb^III–TIAPy (TBAPy: 1,3,6,8-tetrakis(p-benzoate)pyrene; TIAPy: 1,3,6,8-tetrakis(3,5-isophthalic acid)pyrene). The coordination structures of these materials have been characterized by means of electrospray ionization mass spectrometry, X-ray diffraction analysis, and thermogravimetric analysis. Moreover, the porous structure of Yb^III–TIAPy has been evaluated by measuring its N₂ adsorption isotherm. The NIR luminescence properties of Yb^III–TBAPy and Yb^III–TIAPy have been examined by acquiring emission spectra and determining emission lifetimes under air or argon and in vacuo. Yb^III–TIAPy exhibited high thermal stability (with a decomposition temperature of 400 °C), intense luminescence (with an emission quantum yield under argon of 6.6 %), and effective oxygen-sensing characteristics. These results suggest that NIR luminescent Yb^III coordination polymers prepared using pyrene derivatives could have applications in novel thermo-stable oxygen sensors.