A Highly Selective and Sensitive Turn-On Fluorescent Chemosensor Based on Rhodamine 6G for Iron(III)

Recently, more and more rhodamine derivatives have been used as fluorophores to construct sensors due to their excellent spectroscopic properties. A rhodamine-based fluorescent and colorimetric Fe³⁺ chemosensor 3’,6’-bis(ethylamino)-2-acetoxyl-2’,7’-dimethyl-spiro[1H-isoindole-1,9’-[9H]xanthen]-3(2H)-one (RAE) was designed and synthesized. Upon the addition of Fe³⁺, the dramatic enhancement of both fluorescence and absorbance intensity, as well as the color change of the solution, could be observed. The detection limit of RAE for Fe³⁺ was around 7.98 ppb. Common coexistent metal ions showed little or no interference in the detection of Fe³⁺. Moreover, the addition of CN⁻ could quench the fluorescence of the acetonitrile solution of RAE and Fe³⁺, indicating the regeneration of the chemosensor RAE. The robust nature of the sensor was shown by the detection of Fe³⁺ even after repeated rounds of quenching. As iron is a ubiquitous metal in cells and plays vital roles in many biological processes, this chemosensor could be developed to have applications in biological studies.     

热力学数据对1, 3-丁二烯燃烧特性的影响

基于G4方法, 计算了1,^{3-丁二烯框架燃烧反应机理中102个物种的热力学数据, 并考察了振动非谐性、 频率校正因子以及受阻内转动对结果的影响. 结果表明, 考虑振动非谐性或采用不同的频率校正因子, 对热力学数据的影响不大; 考虑内转动后, 对热力学数据有较大影响. 而且考虑内转动后, 得到的热力学数据与实验热力学数据吻合得更好. 用所得热力学数据模拟了1,3-丁二烯的绝热燃烧温度以及点火延迟时间, 结果显示, 要得到可靠的绝热火焰温度, 对小分子(如CO和CO₂等)的热力学数据需要采用实验结果. 将用所得热力学数据模拟得到的点火延迟时间, 与机理本身的热力学数据所得点火延迟时间进行对比, 二者差别显著, 表明所得热力学数据主要通过改变一些反应的逆反应速率常数来影响点火延迟时间. 进一步确定了用所得热力学数据对点火延迟时间有显著影响的一些物种.}     

Recent advances in microbial fuel cell-based toxicity biosensors: Strategies for enhanced toxicity response

Microbial fuel cells (MFCs) have been extensively studied as self-powered toxicity biosensors; however, their applications are limited by the relatively poor toxicity responses. The toxicity responses are known to be related to the factors such as the resistance of species to toxicants, the bioavailability of toxicants and the type of sensing elements. Accordingly, some strategies have already been proposed to enhance the toxicity responses in the past several years, including the external resistance tuning, quorum sensing effect, shear stress control, nutrient level control, electrode material choice, sensing element choice, and cell configuration design. This work introduces and discusses these strategies, and the suggestion for future work is also provided finally.     

Triple-Layered Metal-Organic Framework Hybrid for Tandem Response-Driven Enhanced Chemotherapy

The precise release of drugs is essential to improve cancer therapeutic efficacy. In this work, a tandem responsive strategy was developed based on a triple-layered metal-organic framework (MOF) hybrid. The MOF nanoprobe was stepwise fabricated with a telomerase-responsive inner, a pH-sensitive MOF filling and H₂O₂-responsive coordination complex shell of Fe³⁺ and eigallocatechin gallate (EGCG). In the tumor microenvironment, the shell was dissociated by endogenous H₂O₂ and simultaneously produced highly reactive hydroxyl radicals by a Fenton reaction. Meanwhile, the released EGCG could downregulate the expression of P-glycoprotein responsible for drug resistance. After the dissociation of the framework by protons, telomerase could trigger the release of the drug from the DNA duplex on the exposed inner shell. By integrating confined drug release, inhibited efflux pump and chemodynamic therapy, the all-in-one chemotherapy strategy was identified with enhanced therapeutic efficacy in drug-resistant cancer cells.     

Tailoring the dielectric properties and energy storage density of 1−x(0.94NaNbO3−0.06SZ)−xBi2O3 through substitution strategy

Energy storage using dielectric capacitors is a growing area of research and development. However, designing a highly performing dielectric capacitor is still a challenge. Despite the excellent results achieved in lead-based dielectrics, lead-free substitutes are essential because of the environmental concerns associated with lead-based products. The lead-free 1?x (0.94NaNbO₃? 0.06SrZrO₃)+ x Bi₂O₃ ceramics abbreviated NNSZ + xB for x = 0.0, 0.05, 0.1, 0.15, and 0.20 was fabricated via solid-state reaction. A recoverable energy density of 2.93 J cm?³ was obtained for NNSZ+0.1B, associated with high thermal stability (25–130 °C), excellent cycling (N = 10⁵), and high efficiency (η) of 83.5%. Moreover, the introduction of Bi₂O₃ significantly improved the electrical insulation (?_r at 1 kHz = 1608 and tan δ = 0.0038) and breakdown strength (380 kVcm?¹) of NNSZ+0.1B by minimizing the formation of sodium, bismuth, and oxygen vacancies. The results obtained in this study provide a benchmark for further investigations on NaNbO₃-based ceramics. More importantly, this study suggests that NNSZ + xB ceramics can be used in pulsed power technology.     

Defect Engineering and Anisotropic Modulation of Ionic Transport in Perovskite Solid Electrolyte LixLa(1−x)/3NbO3

Solid electrolytes, such as perovskite Li_3xLa_2/1−xTiO₃, Li_xLa_(1−x)/3NbO₃ and garnet Li₇La₃Zr₂O₁₂ ceramic oxides, have attracted extensive attention in lithium-ion battery research due to their good chemical stability and the improvability of their ionic conductivity with great potential in solid electrolyte battery applications. These solid oxides eliminate safety issues and cycling instability, which are common challenges in the current commercial lithium-ion batteries based on organic liquid electrolytes. However, in practical applications, structural disorders such as point defects and grain boundaries play a dominating role in the ionic transport of these solid electrolytes, where defect engineering to tailor or improve the ionic conductive property is still seldom reported. Here, we demonstrate a defect engineering approach to alter the ionic conductive channels in Li_xLa_(1−x)/3NbO₃ (x = 0.1~0.13) electrolytes based on the rearrangements of La sites through a quenching process. The changes in the occupancy and interstitial defects of La ions lead to anisotropic modulation of ionic conductivity with the increase in quenching temperatures. Our trial in this work on the defect engineering of quenched electrolytes will offer opportunities to optimize ionic conductivity and benefit the solid electrolyte battery applications.     

Diels–Alder Polymer Networks with Temperature‐Reversible Cross‐Linking‐Induced Emission

A novel synthetic strategy gives reversible cross‐linked polymeric materials with tunable fluorescence properties. Dimaleimide‐substituted tetraphenylethene (TPE‐2MI), which is non‐emissive owing to the photo‐induced electron transfer (PET) between maleimide (MI) and tetraphenylethene (TPE) groups, was used to cross‐link random copolymers of methyl (MM), decyl (DM) or lauryl (LM) methacrylate with furfuryl methacrylate (FM). The mixture of copolymer and TPE‐2MI in DMF showed reversible fluorescence with “on/off” behavior depending on the Diels–Alder (DA)/retro‐DA process, which is easily adjusted by temperature. At high temperatures, the retro‐DA reaction is dominant, and the fluorescence is quenched by the photo‐induced electron transfer (PET) mechanism. In contrast, at low temperatures, the emission recovers as the DA reaction takes over. A transparent PMFM/TPE‐2MI polymer film was prepared which shows an accurate response to the external temperature and exhibited tunable fluorescent “turn on/off” behavior. These results suggest the possible application in areas including information security and transmission. An example of invisible/visible writing is given.     

Theranostic Approach for the Protein Corona of Polysaccharide Nanoparticles

Polysaccharide nanoparticles are promising materials in the wide range of disciplines such as medicine, nutrition, food production, agriculture, material science and others. They excel not only in their non‐toxicity and biodegradability but also in their easy preparation. As well as inorganic particles, a protein corona (PC) around polysaccharide nanoparticles is formed in biofluids. Moreover, it has been considered that the overall response of the organism to nanoparticles presence depends on the PC. This review summarises scientific publications about the structural chemistry of polysaccharide nanoparticles and their impact on theranostic applications. Three strategies of implementation of the PC in theranostics have been discussed: I) Utilisation of the PC in therapy; II) How the composition of the PC is analysed for specific disease markers; III) How the formed PC can interact with the immune system and enhances the immunomodulation or immunoelimination. Thus, the findings from this review can contribute to improve the design of drug delivery systems. However, it is still necessary to elucidate the mechanisms of nano‐bio interactions and discover new connections in nanoscale research.     

CT检查参数对腰椎管狭窄症的诊断价值及与疗效、腰椎功能改善的相关性分析

选取我院60例腰椎管狭窄症(LSS)患者作为研究组,同期健康者60例作为对照组,探究CT检查参数对LSS的诊断价值及与疗效、腰椎功能改善的相关性。结果显示,研究组椎管面积、硬膜囊面积、椎管矢径、椎管横径、侧隐窝矢径、侧隐窝角小于对照组(P<0.05);CT各参数联合诊断LSS的AUC值大于任一参数单独诊断;疗效优良患者术后3个月椎管面积、硬膜囊面积、椎管矢径、侧隐窝矢径、侧隐窝角大于治疗前及非优良患者(P<0.05);经偏相关性分析发现,CT检查参数与疗效显著相关(P<0.05)。说明LSS疗效、腰椎功能改善情况与椎管面积、硬膜囊面积、椎管矢径等关系密切,CT检查对指导临床完善手术方案有重要意义。     

Theoretical investigation of nonlinear optical behavior for rod and T-Shaped phenothiazine based D-π-A organic compounds and their derivatives

The exploration of novel materials with excellent nonlinear optical (NLO) features is an area of frontline investigation for scientific community from technological point of view. This study reports the novel phenothiazine-based rod-shaped and T-shaped NLO molecules which are quantum chemically designed from synthesized compounds: rod-shaped (CFA and CBA) and T-shaped (CTA, CCA and CPA). Structural tailoring was performed on D-π-π-A centered CPA chromophore and the effect of various π-spacers, as well as solvents on NLO response properties is investigated. Density functional theory (DFT) along with time dependent DFT (TDDFT) calculations have been executed at B3LYP/6-311G(d,p) functional to examine entire analysis. Results showed a smaller energy gap in structurally modified compounds as compared to reference CPA. Global reactivity parameters analysis revealed smaller hardness and larger softness values in T-shaped compounds. UV–Vis analysis of investigated molecules displayed a red shift in absorption maximum value as compared to CPA. Natural bond orbital (NBO) and frontier molecular orbital (FMO) analysis revealed the stability and intra-molecular electron transferring (ICT) process in investigated molecules. ICT showed the effective charge shift from donor to acceptor via π-spacers. Overall, promising NLO response exists in gas phase and different solvents (acetonitrile, ethyl alcohol and water). Interestingly, proposed molecule CPP presented a maximum value of linear polarizability < α > as 1518.23 a.u and first hyperpolarizability (β_tot) as 755322.39 a.u in acetonitrile solvent. In short, entitled chromophores exhibited excellent NLO properties due to their lower charge transport resistance. This NLO study may open a new topic for researchers to discover novel NLO for hi-tech submissions of modern era.