Straightforward synthesis of fucoxanthin short-chain derivatives via modified-Julia olefination

Fucoxanthin is an essential pigment for the light-harvesting of aquatic algae. It exhibits high energy transfer efficiencies to Chl a (>80%) as well as peridinin (>95%). In order to verify the generality and specificity of the noticeable observation on the ICT excited energy state character, which was found in the study of peridinin, we achieved the straightforward synthesis of a series of fucoxanthin short-chain derivatives via the modified-Julia olefination with the aldehyde half segment possessing a β,γ-epoxyketone function. The established method was successfully applied to the synthesis of the epoxy olefin derivative as an allene modified fucoxanthin analogue.     

Isolation of fucoxanthin from edible brown algae by microwave-assisted extraction coupled with high-speed countercurrent chromatography

A rapid and efficient method for the separation and purification of fucoxanthin from edible brown algae by microwave-assisted extraction coupled with high-speed countercurrent chromatography was developed. The algae were first extracted using microwave-assisted extraction, then the dried extract was dissolved and directly introduced into the high-speed countercurrent chromatography system with a two-phase solvent system consisting of hexane-ethyl acetate-ethanol-water (5:5:6:4, v/v/v/v). The isolation was done in less than 75 min, and a total of 0.83 mg, 1.09 mg, and 0.20 mg fucoxanthin were obtained from 25.0 g fresh Laminaria japonica Aresch, 1.5 g dry Undaria pinnatifida (Harv) Sur, and 15.0 g dry Sargassum fusiforme (Harv) Setch, respectively. The purity of fucoxanthin determined by HPLC was over 90% and its structure was further identified by LC-ESI-MS and (1) H-NMR.     

Excited State Properties of Fucoxanthin Aggregates

The structure and excited state properties of the H- and J-aggregates of the marine carbonyl carotenoid, fucoxanthin(Fx), were studied by various spectroscopic methods, and compared with those of Fx monomers in polar organic solvents. The fluorescent analysis indicated tliat the higher vibronic states of S2 contribute more to populating the S1 state, from which fluorescent emission mainly originates. Resonance Raman and density functional theory calculations confirmed the ‘card-packed' and chead-to-taiF structures of the H- and J-aggregates of Fx, respectively. An fs time-resolved absorption study proved the coexistence of Si and intramolecular charge transfer relaxation pathways upon excitation to the S2 state for both tlie monomers and aggregates.     

Optimization and kinetic modeling of ultrasonic-assisted extraction of fucoxanthin from edible brown algae Sargassum fusiforme using green solvents

The development of green and sustainable extraction technologies for various naturally active biomaterials is gaining increasing attention due to their environmentally friendly advantages. In this work, the ultrasonic-assisted extraction of fucoxanthin from edible brown algae Sargassum fusiforme using different green solvents was presented. Ethyl lactate, limonene, soybean oil, and sunflower oil were used in place of traditional organic solvents. Ethyl lactate showed similar performance to organic solvents, whereas limonene and vegetable oil exhibited higher selectivity for fucoxanthin. Moreover, the effects of various extraction factors, including liquid/solid ratio, extraction time, extraction temperature, as well as amplitude were studied. The optimal conditions were optimized as follows: liquid/solid ratio, 40 mL/g; extraction time, 27 min; extraction temperature, 75 ℃; amplitude, 53%; and solvent, ethyl lactate. Optimal model of second-order kinetic parameters (rate constant, equilibrium concentration, and initial extraction rate) was successfully developed for describing the dynamic ultrasonic extraction process under different operating conditions.     

溶液中光诱导产生岩藻黄质自由基正离子的动力学机制

对比研究了岩藻黄质(Fuc)在氯仿和甲醇溶液中光诱导生成自由基正离子(Fuc·+)的动力学过程,考察了2种不同溶剂中Fuc·+产生机制的差异.采用光谱电化学方法结合纳秒时间分辨吸收光谱技术,通过比较直接光激发和三重态敏化2种不同方式诱导生成Fuc·+的动力学过程发现,在氯仿溶液中Fuc·+主要源于Fuc的单重激发态(S2),在甲醇溶液中则主要源于Fuc的三重激发态(T1).     

Fabrication of fucoxanthin/2-hydroxypropyl-β-cyclodextrin inclusion complex assisted by ultrasound procedure to enhance aqueous solubility,stability and antitumor effect of fucoxanthin

Fucoxanthin (Fx) possesses multiple bioactivities such as antitumor, antioxidant and anti-inflammatory activities, but its application is limited due to the poor water solubility, low bioavailability, and instability to some external harsh conditions. In this study, a stable inclusion complex of Fx and 2-hydroxypropyl-β-cyclodextrin (2-HP-β-CD) was prepared with the aid of ultrasound, which was characterized by scanning electron microscope, Fourier transform infrared spectroscopy, powder X-ray diffraction, and differential scanning calorimetry techniques. The phase solubility analysis and absorption spectroscopy results showed that Fx formed stoichiometry 1:2 inclusion complex with 2-HP-β-CD, and this could be well proved by molecular simulation. Structural analyses and molecular docking study indicated that Fx was successfully encapsulated into the cavity of 2-HP-β-CD, promoting it soluble in water and stable against heat, storage and gastrointestinal environments. In addition, Fx/2-HP-β-CD inclusion complex exhibited excellent antitumor activity against HCT116 and Caco-2 cell lines with IC₅₀ values of 12.0 μΜ and 14.86 μΜ, respectively. Therefore, it could be a potentially promising way to promote the application of Fx in pharmaceuticals and functional foods by HP-β-CD encapsulation strategy.