基于新工科理念的应用化学专业创新创业能力培养体系建设

为了适应新技术、新业态的发展需要,增强学生创新知识转化能力和创新创业能力,推进辽宁省和精细化工行业的技术发展和产业升级,我校依据专业优势、地域特色及社会需求,建立了适应新工科人才培养要求的创新创业培养体系,并对应用化学专业的办学定位、人才培养目标以及教学模式、平台建设、创新创业教育进行了系统设计和全方位改革,取得了一些成效和经验。

Enhanced charge separation by incomplete calcination modified co-doped TiO_(2)nanoparticle for isothiazolinone photocatalytic degradation

Photocatalytic oxidation techniques are promising for degradation of the highly ecotoxic and refractory isothiazolinone bactericides in relevant industrial wastewaters.However,low charge separation and directional transport efficiency under solar light radiation restrain their practical application.Here,we report a nanostructured photocatalyst doped with Gd and B in TiO_(2)with carbon incorporation and defect formation through incomplete calcination.The specific surface area,grain size,and hydrophilicity of TiO_(2)are improved,which is beneficial for the interfacial reaction between the photocatalyst and pollutants.The reduction of the bandgap,the broadening of the photo-absorption range,and the retarded electron-hole recombination promote the photocatalytic performance due to the improved oxygen vacancies based on the electron distribution modification.The difference in partial density of states(ΔPDOS)between the current catalyst and raw TiO_(2)indicates that the co-doping of Gd and B with incomplete calcination changes the electronic hybridization of conduction band and valence band near the Fermi level,and affects the band gap energy.It improved charge separation and directional transport efficiency and benefited the formation of main active species,including•OH and O2•−,for the pollutant decomposition.The rate of photocatalytic removal of benzisothiazolinone(BIT)by the current photocatalyst reaches 1.25 h^(−1),being 4.31 times that of TiO_(2).The current work offers a constructive approach to the design and synthesis of nanostructured photocatalysts for the photocatalytic degradation of refractory organic pollutants.

Engineering J-aggregates for NIR-induced meso-CF_(3)-BODIPY nanoparticles by activated apoptosis mechanism in photothermal therapy

Forming J-aggregates by organic monomer is a fascinating strategy to urge spectroscopic redshift with respect to that of the monomer.Herein,we designed 1,7-diphenyl-substituted meso–CF_(3)-BDP monomer confirmed by X-ray crystallographic analysis.The low-barrier rotation of the–CF_(3)group in meso–CF_(3)-BDP1 significantly enhances the non-radiative efficiency,and the photothermal conversion efficiency(PCE)of the self-assembled nanoparticles(1-NPs:λ_(abs)=746 nm)by J-aggregates was 82%.1-NPs could effectively block cell cycle progression,inhibit cancer cell proliferation and trigger cell apoptosis under low power laser irradiation(0.2 W/cm^(2)).This study proposes an alternate molecular design platform by J-aggregates to promote PCE through the insertion of rotating segment and trigger the cancer cells apoptosis in photothermal therapy at low power laser density.

Development of functional dye with redshifted absorption based on Knoevenagel condensation at 1-site in phenyl[b]-fused BODIPY

Integrating ring-fused modification withπ-conjugated extension is an effective approach for designing,synthesizing,and application for novel borondipyrromethene(BODIPY)structures.In this work,based on phenyl[b]-fused BODIPY,we made reasonable modification of the methyl group at 1-site to generate dye NBDP.NBDP possessed near-infrared region(NIR)absorption and emission properties,and the intramolecular charge transfer(ICT)resulted in low fluorescence.Whereas,heat energy is evidently released in the presence of light,which can be exploited for intracellular photothermal therapy via the cell apoptosis process,reducing the inflammatory side-effects induced by necrosis.This research provides a crucial foundation for the novel molecule via BODIPY multi-directional alteration and its potential application in anti-tumor phototherapy.

Stimulating and harnessing circularly polarized luminescence of helically assembled carbonized polymer dots via interfacial dynamics

Stimulating and harnessing circularly polarized luminescence(CPL)is not only a sine qua non for fundamentally unveiling chirogenesis in physical chemistry,but also a pivotal prerequisite for implementation of such phenomenon in research fields including chiral optoelectronics and theranostics.Herein,red-emissive carbonized polymer dots(CPDs)-based helical structures were synthesized in this work via biomolecule-tailored organic–inorganic co-assembly strategy.The surface statesrelated chirality exhibits enhanced circular dichroism(CD)and CPL activities with anisotropic factors as high as gCD,max=5.4×10^(−3) and glum,max=1.5×10^(−2),respectively.The obtained CPL signals can be further manipulated in an excitationdependent manner,indicating that a synergistic-competition phenomenon exists between configurational chirality and intermolecular energy-transfer dynamics,which is further supported by simulations based on density function theory(DFT).Such tunable CPL behavior triggers revolutionary designs and applications of these chiral CPDs into the realm of chirality-related biological issues and next-generation chiral optoelectronics.

A BODIPY-based Fluorescent Probe for Thiophenol

Thiophenol has been listed as one of the main sources of pollution. Sensitive probes for thiophenol are very significant. Herein, a BODIPY-based fluorescent probe, named BDP, for poisonous thiophenol detection has been reported. BDP shows rapid response （15 s） and clear fluorescence enhancement （30 folds） to thiophenol in solution. The intensity of fluorescence and concentration of thiophenol have a good linear relationship. The detection limit is as low as 13.6 nmol·L^-1： BDP is stable towards pH and light radiation. Cell experiments demonstrate that BDP has good cell membrane penetrability, low cell toxicity and excellent imaging properties in living cells. Therefore, BDP has significant value on the detection of thiophenol in solution and in living cell.

Emulsification for castor biomass oil

The effect of the emulsifier formula on the stability of castor oil-water system was studied through compounding three groups of emulsifiers from the aspects of stability factor of absorbance,centrifuge stability,demulsification time in quiescence,appearance of the droplets,and viscosity.The best emulsifier formula for castor biomass oil was the composite formula of sorbitan monooleate and polyoxyethylene sorbitan monostearate.Correlation exists between the stability of emulsion and the viscosity/particle size of the droplets,with better stability in the case of greater viscosity or narrower distribution of particle size in the emulsion of castor oil-water system.Methanol added to the castor oil-water system may decrease the viscosity of the emulsion.Comparing the castor oil-water emulsion with methanol-castor oil-water emulsion,the optimal hydrophilic and lipophilic balance(HLB)value based on castor oil-water system was acquired between 6.6 and 7.5,while the optimal HLB value based on the methanol-castor oil-water system was between 5.5 and 6.0.The optimal HLB value of methanolcastor oil-water system gradually moved to that of castor oil-water emulsion with adding more water.

Near-infrared absorbing(>700 nm)aza-BODIPYs by freezing the rotation of the aryl groups

The typical aza-BODIPYs in the dye family are known for bright fluorescence,excellent stability,and tunable absorption wavelengths.Hence,these dyes are attracting the increasing attention.Aza-BODIPYs having the maxima absorption in the near-infrared(NIR)region(650-900 nm)are very favorable for bioimaging in vivo due to the less photo-damage,deeper tissue penetration,and less interference from background auto-fluorescence by biomolecules in the living systems.Many strategies have been employed to modify the structures of the aza-BODIPY core to provide the NIR absorbing dyes.Among these,the most effective method is the fusion of the aromatic rings in aza-BODIPY system.This review allsidedly summarizes the recent development of ring-fused aza-BODIPY dyes(λ_(abs)>700 nm)focusing on the design,synthesis,and potential applications in the NIR region since 2002.

Preparation and photocatalytic kinetics of nano-ZnO powders by precipitation stripping process

Ultra-fine zinc oxalate powders were prepared through a precipitation stripping method with bis(2-ethylhexyl)phosphate(HDEHP)diluted by tetrachloride carbon as the extractant,and oxalic acid ethanol aqueous solution as the re-extractant and precipitator.Zinc oxide powders were obtained by decomposing zinc oxalate powders at 450℃.The prepared zinc oxide powders were characterized by transmission electron microscope(TEM),Scanning electron microscope(SEM),Thermogravimetric analysis(TG),X-ray diffraction(XRD)and Fourier transmission infrared(FT-IR)spectrum.The photocatalytic performance of methylene blue by zinc oxide was studied based on the Langmuir model and Photo-Layer model.The results show that some zinc oxide powders were micro-multipore materials with hexagonal crystal.The particle size was around 32 nm.The photocatalytic process was the control step in the chemical reaction.The photo catalytic process followed pseudo-first order kinetics and NOH concentration inside the photo-layer in different reaction condition were calculated according to the Photo-Layer model.