Synthesis of Hydrophilic Derivative Surfactants From Algae-Derived Unsaponifiable Lipids

In the context of decarbonizing the economy, the utilization of biologically sourced feedstocks to produce replacements for petroleum-derived materials is becoming more urgent. Improving renewable biomass production and utilization is imperative for commercializing future biorefineries. Algae-derived biomass is a particularly promising feedstock thanks to its attractive oil content and composition; specifically, the high-value products in the unsaponifiable lipids have not been included in a conversion process. Here we demonstrate surfactant synthesis from a complex oil fraction as the hydrophobic donor moieties, yielding products that are similar to commercially available surfactants such as the linear alkyl benzene sulfonates. Unsaponifiable lipids extracted from algae were derivatized to non-ionic surfactants using a green chemical synthesis route based on a double esterification with succinic acid and polyethylene glycol. The in-depth molecular and structural surfactant characterization is included and indicates that the resulting properties fall between those of pure cholesterol and phytol used as surrogates for the reaction synthesis demonstration. This is the first demonstration of an effective and potentially high-value synthesis of functional surfactants with properties that can be tailored based on the relative composition of the resulting hydrocarbon alcohol components in the mixture. This novel green chemistry synthesis approach provides a route to high-value product synthesis from algae.

Evaluation of bile duct stones extracted by ERCP (Endoscopic Retrograde Cholangio-Pancreatography).

Objective: To determine the frequency of different types of gallstones on ERCP stone extraction from bile duct. Study Design: Cross Sectional study. Setting: Department of Gastroenterology of the Nishtar Hospital Multan. Period: September 2019 to October 2020. Material & Methods: Patients with bile duct stones on imaging of either sex aged 18 – 70 years were included in our study while patients with IHD, malignancies, liver cirrhosis, asthma, TB, COPD, ILD and pregnant women were excluded from our study. During ERCP the gross appearance of extracted stones and related findings were noted. Results: Our study included 139 patients meeting inclusion criteria, of these 139 study cases, 49 (35.3%) were male and 90 (64.7%) were female patients with bile duct stone. Mean age was 45.78 ± 12.05 year (range; 27 – 68 years). Of these 139 study cases, 56 (40.3%) were from rural areas, 83 (59.7 %) were from urban areas, 52 (37.4%) had poor socioeconomic status and 87 (62.6%) were from middle income family background. Diabetes was noted in 35 (25.2%), hypertension in 53 (38.1%) and obesity in 32 (23 %) (Mean BMI was 26.53±214kg/m2). Mean stone size in our study was 15.82 ± 6.34 mm while 78 (56.12 %) had single stones. Pure cholesterol gallstones were noted in 47 (33.8%), mixed cholesterol stones in 71 (51.1%) and brown pigmented gall stones in 21 (15.1%). Conclusion: Mixed cholesterol stones were more frequent followed by pure cholesterol and brown pigmented stones in bile duct gallstones patients. Mixed cholesterol stones were significantly associated with rural residential status and hypertension while brown pigmented stones were residential status, hypertension and obesity.

Simultaneous Synthesis of Vitamins D2, D4, D5, D6, and D7 from Commercially Available Phytosterol, β-Sitosterol, and Identification of Each Vitamin D by HSQC NMR

We succeeded in simultaneously synthesizing the vitamin D family, vitamins D2, D4, D5, D6, and D7, from β-sitosterol, which is sold as a commercially available reagent from Tokyo Chemical Industry Co., Ltd. It is officially sold as a mixture of four phytosterols {β-sitosterol (40–45%), campesterol (20–30%), stigmasterol, and brassicasterol}. Owing to this, we anticipated that, using this reagent, various vitamin D analogs could be synthesized simultaneously. We also synthesized vitamin D3 from pure cholesterol and analyzed and compared all vitamin D analogs (D2, D3, D4, D5, D6, and D7) by HSQC NMR. We succeeded in clearly demonstrating the difference in the NMR chemical shifts for each vitamin D analog.

Why Is Very High Cholesterol Content Beneficial for the Eye Lens but Negative for Other Organs?

The plasma membranes of the human lens fiber cell are overloaded with cholesterol that not only saturates the phospholipid bilayer of these membranes but also leads to the formation of pure cholesterol bilayer domains. Cholesterol level increases with age, and for older persons, it exceeds the cholesterol solubility threshold, leading to the formation of cholesterol crystals. All these changes occur in the normal lens without too much compromise to lens transparency. If the cholesterol content in the cell membranes of other organs increases to extent where cholesterol crystals forma, a pathological condition begins. In arterial cells, minute cholesterol crystals activate inflammasomes, induce inflammation, and cause atherosclerosis development. In this review, we will indicate possible factors that distinguish between beneficial and negative cholesterol action, limiting cholesterol actions to those performed through cholesterol in cell membranes and by cholesterol crystals.

X-ray microtomography setup for absorption and diffraction tomography

The results of studying silicon single crystals and gallstones on a laboratory X-ray microtomograph with a spatial resolution of 10 µm (developed at the Federal Scientific Research Centre for «Crystallography and Photonics» of the Russian Academy of Sciences) are reviewed. The method of tomographic experiment included the use of a monochromatic «parallel beam» with subsequent three-dimensional reconstruction based on a set of two-dimensional projections. Topotomographic measurements were performed in the mode of rotation of the samples under study around the normal to the reflecting plane adjusted to the Laue diffraction reflection geometry, which made it possible to identify and study single dislocations in perfect silicon crystals. Simulation of the dislocation loops was carried out on the basis of numerical solution of the Takagi-Taupin equations. In-vitro microtomographic study of human gallstones revealed the layered structure of the gallstones which are close in composition to modifications of calcium carbonate. The internal structure of the stones is heterogeneous and contains numerous cavities and cracks formed upon their growth. At the same time, the evaluation of the porosity of gallstones is necessary, since the latter can affect the rate of stone dissolution in their treatment by litholytic methods. Linear attenuation coefficients of x-ray radiation of cholesterol-type gallstones were calculated from the measurement results. The good agreement of the experimentally obtained results and calculations based on tabular data for pure cholesterol is demonstrated which proved that the tomographic method can be used for in vivo diagnosis of cholesterol-type gallstones.

Structural Characterization of Gallbladder Stones Using Energy Dispersive X-ray Spectroscopy and X-ray Diffraction

Aim and Objective: Formation of the gallbladder stones is a common disease and a major health problem. The present study aimed to identify the structures of the most common types of gallbladder stones using X-ray spectroscopic techniques, which provide information about the process of stone formation. Material and Method: Phase and elemental compositions of pure cholesterol and mixed gallstones removed from gallbladders of patients were studied using energy-dispersive X-ray spectroscopy combined with scanning electron microscopy analysis and X-ray diffraction. Results: The crystal structures of gallstones which coincide with standard patterns were confirmed by X-ray diffraction. Plate-like cholesterol crystals with laminar shaped and thin layered structures were clearly observed for gallstone of pure cholesterol by scanning electron microscopy; it also revealed different morphologies from mixed cholesterol stones. Elemental analysis of pure cholesterol and mixed gallstones using energy-dispersive X-ray spectroscopy confirmed the different formation processes of the different types of gallstones. Conclusion: The method of fast and reliable X-ray spectroscopic techniques has numerous advantages over the traditional chemical analysis and other analytical techniques. The results also revealed that the X-ray spectroscopy technique is a promising technique that can aid in understanding the pathogenesis of gallstone disease.