Design,Synthesis And Application Of Cationic Fluorescent Dyes Based On Cyanine Derivates

With the development of the society,science and the technology,more and more requirements will be suggested to limit the application of the fluorescent dyes-especially for the textile application.For example,people hope that the fluorescent dyes are friendly to human body and environment with high quantum yield.In further,photo-stability,limit the application of the fluorescent dyes,of some fluorescent dyes should be improved.Styrene pyridine salt fluorescent dyes,although,are popular in biomedicine since it not only has good fluorescent properties but also has broad range of absorption wavelength,it is hardly used in textile since the bad photo-stability.Meanwhile,as the development of the computer technology,many auxiliary science softwares-such as Gaussian,Material studio,Molcas and so on-were designed and improved to help researchers to study the different knowledge in the different fields,such like electrical,dyes,crystal,etc.al,because the developed computer programs can predict the physical and chemical properties of compounds and materials accurately.With the assistant of the developed computer programs,many complex experiments could be avoided,and much time could be saved.The purpose of this manuscript was design and synthesis fluorescent dyes with good photo-stability.Studying the fluorescent properties of the designed fluorescent dyes could be simplified with the assistant of the developed computer programs,while it also can provides theoretical support for experiments.The main contents and conclusions were listed as following words:1.Some commercial and reported fluorescent dyes were collected,summarized and analyzed from the websites and published papers.In order to classify the fluorescent dyes clearly,both of the fluorescence intensity and quantum yield were adopted to range the fluorescent dyes in this manuscript.Fluorescent dyes with high fluorescence intensity and fluorescence quantum yield between 0.8 and 1.0 were selected.ECOSAR 2.0 was adopted to estimate the bio-toxicity of the selected fluorescent dyes.The analyzed results illustrated that the sulfonic,hydroxyl and carboxyl groups can decrease the bio-toxicity of chemicals,while the Br can increase the chemicals' bio-toxicity.The fluorescent dyes,classified as very intense and environmental friendly,were analyzed by Hansen solubility parameters(HSP)to study their dyeing properties.The results shown that the five environmental friendly fluorescent dyes with high quantum yield could dye five kinds of fibers in this manuscrtipt,but the dyeing properties of them were different to each other.In order to verify the accuracy of the prediction,romdamine B was adopted to dye PET fiber,the results shown that rhodamine B can not color the PET fiber by using traditional cationic dyes dyeing procedure,but when the dye temperature was rose up to 130?,rhodamine B color PET fiber with obvious fluorescence,obviously.DFT method was adopted to calculate the maximum absorption wavelength and maximum emission wavelength of the N-methylacridinium,the calculated results were close to the data in the reference.2.A hemicyanine fluorescent dye(styrene pyridinium salt,DYE-BD)was synthesiszed.Gaussian 09 was adopted to calculate the enthalpy and Gibbs free energy of chemicals,while the DFT and TD-DFT were adopted to simulate UV/VIS and fluorescence spectral of DYE-BD,the results shown that the DFT and TD-DFT can calculate the maximum absorption wavelength and maximum emission wavelength accurately,but the different methods gave different errors.For the DYE-BD,b31yp/dgdzvp2 gave more creditable maximum emission wavelength-closer to the experiment data.While the maximum absorption wavelength calculated by pbe0/6-311+g(d,p)was closer to the real data.Mathematic modle was established to study the energy change in the fluorescence process,while the quantum method was adopted to analyze the photo-stability of the DYE-BD.3.Five different hemicyanine fluorescent dyes were designed with different substituent groups.The enthalpy,gibbs free energy,maximum absorption wavelength and maximum emission wavelength of the chemicals were calculated by Gaussian 09.The results simulated by Gaussian 09 shown that 6(include parent dye)hemicyanine dyes can be synthesized by Knoevenagel condensation reaction,and all of the designed dyes could emit fluorescence after excited by relevant photon.The bio-toxicity of the designed dyes were analyzed by ECOSAR 2.0,while four of them were environmental friendly.Both sulfonic and carboxyl group could decrease the bio-toxicity of the chemicals.The sulfonic group could decrease the bio-toxicity of the chemicals ignoring the positions,while the sulfonic group was more effective than carboxyl group.Quantum method was adopted to study the photo-stability of the dyes.Z2 and Z5 were synthesized to illustrate the creditable of the results predicted by computer program.The experiment illustrated that Z2 and Z5 have obvious fluorescence,while the maximum absorption wavelength and maximum emission wavelength of Z5 were close to the simulate data.Z2 had better photo-stability than Z5 and it had low toxicity.Both of Z2 and Z5 could dye PET fabric under 130?.4.Three hemicyanine fluorescent dyeswith carboxyl groups were synthesized and grafted to the O-CMC.The macromolecular skeleton was used to improve the photo-stability of the parent fluorwscent dye.The results shown that the three polymeric dyes have obvious fluorescence.The macromolecular skeleton could improve the photo-stability of the parent dye.But for the different parents dyes,macromolecules skeleton have different effects in improving their photo-stability.Macromolecular skeleton can improve the photo-stability of the parent dye with bad photo-stability,effectively.But for parent dye with better photo-stability,the influence of the macromolecular skeleton is relatively small.5.A parent hemicyanine fluorescent dye B with carbon double bond was designed and synthesized.Gaussian 09 was adopted to predict the absorption and emission spectral of the parent dye B,while the simulate data was close to the real data.Different solvents had different affection on the maximum absorption wavelength and maximum emission wavelength of the dye B,the results shown that the maximum absorption wavelength was decrease as the increased polarity of the solvent,but the stokes shift were increased following the increased polarity of the solvent.The parent fluorescent dye B was copolymerized with acrylamide,HEMA and methyl methacrylate to form the polymeric dyes,the experiment results shown that water solution of P-B-AM had obvious fluorescence,but the fluorescence intensity of the P-B-AM was lower than that of P-B-AM-HEMA and P-B-HEMA.The fluorescence intensity of water solution of P-B-AM was low,while the fabric printed by P-B-AM didn't have obvious emission peak.Thus,the fluorescent properties of P-B-AM was bad.According to the results,the P-B-AM-HEMA and P-B-HEMA had better photo-stability than parent dye,while the photo-stability of P-B-HEMA was better than P-B-AM-HEMA.Due to the different weight of molecular,P-B-AM-HEMA could dye acrylic fabrics,while P-B-HEMA could't dye acrylic fabrics,so,P-B-HEMA coating the acrylic fabrics;Polymer,used for electrospinning,was formed by parent fluorescent dye B,HEMA and MMA.The results shown that the polymers were successesed used for electrospinning when the concentration was 0.5g/mL,respectively.While the water solution and spun fiber membranes had obvious fluorescence.