Rational Molecular Design towards Vis/NIR Absorption and Fluorescence by using Pyrrolopyrrole aza‐BODIPY and its Highly Conjugated Structures for Organic Photovoltaics

Pyrrolopyrrole aza‐BODIPY (PPAB) developed in our recent study from diketopyrrolopyrrole by titanium tetrachloride‐mediated Schiff‐base formation reaction with heteroaromatic amines is a highly potential chromophore due to its intense absorption and fluorescence in the visible region and high fluorescence quantum yield, which is greater than 0.8. To control the absorption and fluorescence of PPAB, particularly in the near‐infrared (NIR) region, further molecular design was performed using DFT calculations. This results in the postulation that the HOMO–LUMO gap of PPAB is perturbed by the heteroaromatic moieties and the aryl‐substituents. Based on this molecular design, a series of new PPAB molecules was synthesized, in which the largest redshifts of the absorption and fluorescence maxima up to 803 and 850 nm, respectively, were achieved for a PPAB consisting of benzothiazole rings and terthienyl substituents. In contrast to the sharp absorption of PPAB, a PPAB dimer, which was prepared by a cross‐coupling reaction of PPAB monomers, exhibited panchromatic absorption across the UV/Vis/NIR regions. With this series of PPAB chromophores in hand, a potential application of PPAB as an optoelectronic material was investigated. After identifying a suitable PPAB molecule for application in organic photovoltaic cells based on evaluation using time‐resolved microwave conductivity measurements, a maximized power conversion efficiency of 1.27 % was achieved.     

Point‐to‐Plane Nonhomogeneous Electric‐Field‐Induced Simultaneous Formation of Giant Unilamellar Vesicles (GUVs) and Lipid Tubes

It is well‐known that homogeneous electric fields can be used to generate giant unilamellar vesicles (GUVs). Herein we report an interesting phenomenon of formation of GUVs and lipid tubes simultaneously using a nonhomogeneous electric field generated by point‐to‐plane electrodes. The underlying mechanism was analyzed using finite element analysis. The two forces play main roles, that is, the pulling force (F) to drag GUVs into lipid tubes induced by fluid flow, and the critical force (Fc) to prevent GUVs from deforming into lipid tubes induced by electric fields. In the center area underneath the needle electrode, the GUVs were found because F is less than Fc in that region, whereas in the edge area the lipid tubes were obtained because F is larger than Fc. The diffusion coefficient of lipid in the tubes was found to be 4.45 μm² s^?1 using a fluorescence recovery after photobleaching (FRAP) technique. The method demonstrated here is superior to conventional GUV or lipid tube fabrication methods, and has great potential in cell mimic or hollow material fabrication using GUVs and tubes as templates.     

N‐(2‐Ethylhexyl)carbazole: A New Fluorophore Highly Suitable as a Monomolecular Liquid Scintillator

The synthesis, photophysical properties, and applications in scintillation counting of N‐(2‐ethylhexyl)carbazole (EHCz) are reported. This molecule displays all of the required characteristics for an efficient liquid scintillator (emission wavelength, scintillation yield), and can be used without any extra fluorophores. Thus, its scintillation properties are discussed, as well as its fast neutron/gamma discrimination. For the latter application, the material is compared with the traditional liquid scintillator BC‐501 A, and other liquid fluorescent molecules classically used as scintillation solvents, such as xylene, pseudocumene (PC), linear alkylbenzenes (LAB), diisopropylnaphthalene (DIN), 1‐methylnaphthalene (1‐MeNapht), and 4‐isopropylbiphenyl (iPrBiph). For the first time, an excimeric form of a molecule has been advantageously used in scintillation counting. A moderate discrimination between fast neutrons and gamma rays was observed in bulk EHCz, with an apparent neutron/gamma discrimination potential half of that of BC‐501 A.     

Thermoresponsive polymersome from a double hydrophilic block copolymer

The article describes synthesis and thermally triggered self‐assembly of a Poly (ethylene oxide)‐block‐poly (N‐insopropylacrylamide) (PEO‐b‐PNIPAm) in aqueous medium. At rt, the polymer remains as unimer, however, at lower critical solution temperature (LCST) of PNIPAm (32 °C), it forms a rather large undefined aggregate which at slightly elevated temperature (～40 °C) converges to well defined polymersome structure (Critical aggregation concentration = 0.45 mg/mL) with hydrodynamic diameter of 40–50 nm. By lowering the temperature, initial swelling of the compact vesicle followed by reversible disassembly to unimer was noticed. The polymersome exhibits encapsulation ability to a hydrophilic dye Calcein which can be spontaneously released by lowering the temperature below cloud point. Likewise a hydrophobic dye namely 8‐Anilino‐1‐naphthalenesulfonic acid (ANS) can also be encapsulated and released by thermal trigger. Detail photoluminescence studies reveal ANS dye can be used as a generalized probe molecule for detecting LCST of a thermoresponsive polymer by “fluorescence on” above LCST even by cursory observation. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2444–2451     

Water‐Soluble Luminescent Hybrid Composites Consisting of Oligosilsesquioxanes and Lanthanide Complexes and their Sensing Ability for Cu2+

Water‐soluble hybrid composites with great potential for selective and sensitive sensing and that are obtained through simple, rapid, and environmentally friendly methods are highly desirable and remain a challenging task. Herein, we present luminescent hybrid composites that were realized by linking Na₃[Ln(dpa)₃] (dpa=2,6‐pyridinedicarboxylic acid) to octa‐amino functionalized polyhedral oligomeric silsesquioxane (POSS‐NH₂) through hydrogen‐bonding interactions between the oxygen atoms of the carboxylate groups of dpa and the hydrogen‐bond‐donor amino groups. The resulting hybrid composites Ln(dpa)₃@POSS‐NH₂ are highly soluble in aqueous solutions and the quantum yield of Eu(dpa)₃@POSS‐NH₂ is as high as 56.5 % or 46.3 % in the solid state and in aqueous solution, respectively, as determined by using the integrating sphere method. The novel water‐soluble luminescent hybrid composites exhibit high thermal and photostability, and the emitted colors of the resulting hybrid composite can be finely tuned by changing the Eu³⁺/Tb³⁺ ratio. Interestingly, Eu(dpa)₃@POSS‐NH₂ hybrid composites exhibited an effective switch‐off fluorescence response to Cu²⁺ over other common metal ions in aqueous media.     

Highly fluorescent polycaprolactones decorated with di(thiophene‐2‐yl)‐diketopyrrolopyrrole: A covalent strategy of tuning fluorescence properties in solid states

Well‐defined 1,4‐diketo‐3,6‐di(thiophen‐2‐yl)pyrrolo[3,4‐c]pyrrole (DTDPP) labeled polycaprolactones (PCL) with different chain lengths were synthesized and characterized. The effect of polymer chain lengths on the optical properties of DTDPP in solid states was studied by UV‐Vis absorption spectroscopy as well as steady‐state and dynamic fluorescence spectroscopies. Our results indicate that when the PCL side chain is extended to a certain length, the intermolecular aggregation of DTDPP units can be reduced significantly due to segregation effect of PCL. This approach offers a new facile strategy to address the common problem of aggregation‐caused quenching existing in organic fluorophores. These highly fluorescent biodegradable PCL polymers may find broad biomedical applications such as fluorescence‐based bioimaging and tissue engineering. © 2015 Wiley Periodicals, Inc. J. Polym. Sci. Part A: Polym. Chem. 2015 , 53, 1032–1042     

Synthesis of polymer with defined fluorescent end groups via reversible addition fragmentation transfer polymerization for characterizing the conformations of polymer chains in solutions

A new type of chain transfer agent used in reversible addition fragmentation chain transfer (RAFT) polymerization named 9‐anthracenylmethyl (4‐cyano‐4‐(N‐carbazylcarbodithioate) pentanoate) (ACCP) was synthesized with a total yield over 75% by the incorporation of both fluorescent donor and acceptor chromophores. Polymerization of heterotelechelic α,ω end‐labeled dye‐functionalized polystyrene (PS), poly(methyl methacrylate) (PMMA), and poly(n‐butyl methacrylate) (PBMA) with adjustable molecular weights and narrow polydispersity could be conducted by a one‐pot procedure through RAFT polymerization with this bischromophore chain transfer agent. The polymerizations demonstrated “living” controlled characteristics. By taking advantage of the characteristic fluorescence resonance energy transfer (FRET) response between the polymer chain terminals, the variation of chain dimensions in solution from the dilute region to the semidilute region can be monitored by changes in the ratio of the fluorescence intensities of the carbazolyl group to the anthryl group, which lends itself to potential applications in characterizing chain dimensions in solutions for thermodynamic or dynamic studies. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2413–2420     

不同抗凝比例对凝血四项检测结果的影响

目的观察并分析凝血四项检测结果与不同比例下的全血与抗凝剂之间的关系。方法研究对象取2015年6月来湖北省宜昌市第二人民医院参加体检的110例健康人员,抽取全血血液样本后按照不同比例与抗凝剂混匀,常规分离血浆并测定受试者凝血酶时间(TT)、凝血酶原时间(PT)、激活部分促凝血酶原激酶时间(APTT)以及纤维蛋白原(FIB),并对研究结果相关数据作统计学处理。结果当血液量与抗凝剂比例为1∶5时,标本TT、PT、APTT以及FIB各项指标较1∶9时差异显著而具有统计学意义(P0.05);抗凝比例1∶7的情况下,TT指标差异与1∶9抗凝比例标本相比差异具有统计学意义(P0.05),而PT、FIB以及APTT三项指标差异并无统计学意义(P0.05);抗凝比例为1∶11与1∶13的情况下,TT指标与1∶9抗凝比例标本相比差异具有统计学意义(P0.05),而PT、FIB以及APTT三项指标差异并无统计学意义(P0.05)。结论凝血四项检测工作中,标本质量检测控制最关键的环节在于准确采集血液量,倘若采集血量过多或过少,导致与抗凝剂比例失调往往会影响测定结果准确性,检验科工作人员应予以重视。     

High‐Level Incorporation of Silver in Gold Nanoclusters: Fluorescence Redshift upon Interaction with Hydrogen Peroxide and Fluorescence Enhancement with Herbicide

High‐level incorporation of Ag in Au nanoclusters (NCs) is conveniently achieved by controlling the concentration of Ag⁺ in the synthesis of bovine serum albumin (BSA)‐protected Au NCs, and the resulting structure is determined to be bimetallic Ag₂₈Au₁₀‐BSA NCs through a series of characterizations including energy‐dispersive X‐ray spectroscopy, mass spectroscopy, and X‐ray photoelectron spectroscopy, together with density functional theory simulations. Interestingly, the Ag₂₈Au₁₀ NCs exhibit a significant fluorescence redshift rather than quenching upon interaction with hydrogen peroxide, providing a new approach to the detection of hydrogen peroxide through direct comparison of their fluorescence peaks. Furthermore, the Ag₂₈Au₁₀ NCs are also used for the sensitive and selective detection of herbicide through fluorescence enhancement. The detection limit for herbicide (0.1 nm ) is far below the health value established by the U.S. Environmental Protection Agency; such sensitive detection was not achieved by using AuAg NCs with low‐level incorporation of Ag or by using the individual metal NCs.     

High‐Energy Long‐Lived Mixed Frenkel–Charge‐Transfer Excitons: From Double Stranded (AT)n to Natural DNA

The electronic excited states populated upon absorption of UV photons by DNA are extensively studied in relation to the UV‐induced damage to the genetic code. Here, we report a new unexpected relaxation pathway in adenine–thymine double‐stranded structures (AT)_n. Fluorescence measurements on (AT)_n hairpins (six and ten base pairs) and duplexes (20 and 2000 base pairs) reveal the existence of an emission band peaking at approximately 320 nm and decaying on the nanosecond time scale. Time‐dependent (TD)‐DFT calculations, performed for two base pairs and exploring various relaxation pathways, allow the assignment of this emission band to excited states resulting from mixing between Frenkel excitons and adenine‐to‐thymine charge‐transfer states. Emission from such high‐energy long‐lived mixed (HELM) states is in agreement with their fluorescence anisotropy (0.03), which is lower than that expected for π–π* states (≥0.1). An increase in the size of the system quenches π–π* fluorescence while enhancing HELM fluorescence. The latter process varies linearly with the hypochromism of the absorption spectra, both depending on the coupling between π–π* and charge‐transfer states. Subsequently, we identify the common features between the HELM states of (AT)_n structures with those reported previously for alternating (GC)_n: high emission energy, low fluorescence anisotropy, nanosecond lifetimes, and sensitivity to conformational disorder. These features are also detected for calf thymus DNA in which HELM states could evolve toward reactive π–π* states, giving rise to delayed fluorescence.