A rapid and multi-endpoint ecotoxicological test using Mychonastes afer for efficient screening of metals and herbicides.

Microalgal growth-based tests are international standards for ecotoxicity assessment; however, their long exposure times, large sample volumes, and reliance on a single growth-endpoint make them inadequate for rapid toxicity screening. Here, we aimed to develop a rapid and simple ecotoxicological test using the fast-growing green alga Mychonastes afer, with multiple endpoints-growth, lipid content, and photosynthesis. We exposed M. afer to two metals-silver and copper-and two herbicides-atrazine and diuron-for 24 h and identified the most sensitive and reliable endpoints for each toxicant: the maximum electron transport rate (ETRmax) for Ag, Cu and atrazine, and the lipid content for diuron. Lipid content was found to be both a sensitive and reliable biomarker, meeting the effluent limit guidelines in both the Republic of Korea and the USA. The sensitivity of M. afer to Ag and atrazine also closely matched the HC5 values derived from the species sensitivity distribution approach, confirming its reliability for setting regulatory concentrations of these contaminants. Our calculated predicted no-effect concentration (PNEC) values were similar to established European Union PNECs for Ag, Cu, atrazine, and diuron, underlining the utility of these biological endpoints for ecological risk assessment and regulatory decision making. This method required lower sample volume (2 mL vs 100 mL) and exposure time (24 h vs 72-120 h) than conventional green algal tests, and eliminated the need for labour-intensive cell counting, expensive equipment, and chlorophyll fluorescence measurement expertise. Overall, this M. afer test can be a valuable tool for the rapid screening of wastewater for metals and herbicides, contributing to environmental protection and management practices.

Recent Progress in Diatom Biosilica: A Natural Nanoporous Silica Material as Sustained Release Carrier.

A drug delivery system (DDS) is a useful technology that efficiently delivers a target drug to a patient's specific diseased tissue with minimal side effects. DDS is a convergence of several areas of study, comprising pharmacy, medicine, biotechnology, and chemistry fields. In the traditional pharmacological concept, developing drugs for disease treatment has been the primary research field of pharmacology. The significance of DDS in delivering drugs with optimal formulation to target areas to increase bioavailability and minimize side effects has been recently highlighted. In addition, since the burst release found in various DDS platforms can reduce drug delivery efficiency due to unpredictable drug loss, many recent DDS studies have focused on developing carriers with a sustained release. Among various drug carriers, mesoporous silica DDS (MS-DDS) is applied to various drug administration routes, based on its sustained releases, nanosized porous structures, and excellent solubility for poorly soluble drugs. However, the synthesized MS-DDS has caused complications such as toxicity in the body, long-term accumulation, and poor excretion ability owing to acid treatment-centered manufacturing methods. Therefore, biosilica obtained from diatoms, as a natural MS-DDS, has recently emerged as an alternative to synthesized MS-DDS. This natural silica carrier is an optimal DDS platform because culturing diatoms is easy, and the silica can be separated from diatoms using a simple treatment. In this review, we discuss the manufacturing methods and applications to various disease models based on the advantages of biosilica.

Environmental factors affecting akinete germination and resting cell awakening of two cyanobacteria.

Globally, cyanobacteria frequently cause blooms that outcompete other species in the waterbody, affecting the diversity, decreasing water exchange rates, and promoting eutrophication that leads to excessive algal growth. Here, Dolichospermum circinale (akinetes) and Microcystic aeruginosa (resting cells), were isolated from the sediment in the Uiam Dam in the North Han River and near Ugok Bridge in the Nakdong River, respectively. The morphology, germination process and rates, and growth was evaluated in different environmental conditions. D. cercinalis germination began on day two of culturing, with maximum cell growth observed on day ten. In contrast, M. aeruginosa exhibited daily increase in cell density and colony size, with notable density increase on day six. Next, different environmental conditions were assessed. Akinetes exhibited high germination rates at low light intensity (5-30 µmol/m2/s), whereas resting cells exhibited high growth rates at high light intensity (50-100 µmol/m2/s). Furthermore, both cell types exhibited optimum germination and growth in media containing N and P at 20-30° at a pH of 7-9. Our study reveals the optimum conditions for the germination and growth of cyanobacterial akinetes and resting cells isolated from river sediment, respectively, and will assist in predicting cyanobacterial blooms for appropriate management.

New recorded diatoms in Holocene sediment cores from the Gonggeom-ji Wetland in Korea.

The Gonggeom-ji reservoir is an agricultural one built for rice farming during the Proto-Three Kingdoms period and was designated as Gyeongsangbuk-do monument No. 121 because of its high historical value. The Nakdonggang National Institute of Biological Resources has been conducting paleontological and paleoenvironmental studies on major wetlands from Korea since 2016, as well as diatom, geological, and depth distribution analyses on the sedimentary soil of Gonggeom-ji. This study summarized the description and ecological characteristics of six newly recorded diatoms (Gomphonema lacusrankala, Pinnularia diandae, P. gibba var. hyaline, P. lacunarum, Sellaphora labda var. nipponica, Stauroneis angustilancea) found in samples collected through drilling in Gonggeom-ji in 2019.

Flocculation kinetics and mechanisms of microalgae- and clay-containing suspensions in different microalgal growth phases.

Interplays between microalgae and clay minerals enhance biologically mediated flocculation, thereby affecting the sedimentation and transportation of suspended particulate matter (SPM) in water and benthic environments. This interaction forms larger flocs with a higher settling velocity and enhances SPM sinking. The aim of this study was to investigate the flocculation kinetics of microalgae and clay in suspension and to elucidate the mechanisms associated with such interactions. Standard jar test experiments were conducted using various mixtures of kaolinite and microalgal samples from batch cultures (Chlorella vulgaris) to estimate biologically mediated flocculation kinetics. The organic matter (OM) composition secreted by the microalgae was characterized using a liquid chromatography - organic carbon detection system, and quantitative analysis of transparent exopolymer particles was conducted separately. A two-class flocculation kinetic model, based on the interaction between flocculi and flocs, was also adopted to quantitatively analyze the experimental data from flocculation. Results from the flocculation kinetic tests and OM analyses, in association with other data analyses (i.e., floc size distribution and flocculation kinetic model), showed that flocculation increased with OM concentration during the growth phase (10-20 d). However, on day 23 during the early stationary phase, flocculation kinetics started decreasing and substantially declined on day 30, even though the amount of OM (mainly biopolymers) continued to increase. Our results indicate that an adequate quantity of biopolymers produced by the microalgal cells in the growth phase enhanced floc-to-floc attachment and hence flocculation kinetics. In contrast, an excessive quantity of biopolymers and humic substances in the stationary phase enhanced the formation of polymeric backbone structures and flocculation via scavenging particles but simultaneously increased steric stabilization with the production of a large number of fragmented particles.

Asynchronous multi-decadal time-scale series of biotic and abiotic responses to precipitation during the last 1300 years.

East Asian summer monsoon (EASM)-driven rapid hydroclimatic variation is a crucial factor with major socioeconomic impacts. Nevertheless, decadal- to centennial-scale EASM variability over the last two millennia is still poorly understood. Pollen-based quantitative annual precipitation (PqPann) and annual precipitation reconstructed by artificial neural networks (ANNs) for the period 650-1940 CE were reconstructed from a paleo-reservoir in South Korea. ANNs reconstruction was performed to compensate for a hiatus section. On a decadal timescale, 10 high-precipitation periods were identified, and PqPann and ANNs reconstructions were comparable to local instrumental rainfall and historic drought records. Biotic lags to rapid climatic changes ranging from 25 to 100 years were recognized by asynchronous pollen and speleothem responses to precipitation. We suggest that PqPann-based decadal- to centennial-scale climatic change reconstruction should take biotic lags into account, although the lags can be ignored on the millennial scale. The position of the EASM rainband influenced rainfall magnitude.

Studies on nanosized iron based modified catalyst for Fischer-Tropsch synthesis application.

To improve catalytic performance iron based catalyst, the effects of some metal promoters, especially potassium, copper and other transition metal oxides as well as different supports have been reported. A series of Fe/K/Cu catalysts promoted with magnesium and ceria by precipitation method, followed by impregnation method; keeping Cu and K content same. The catalysts were characterized by XRD, N2 physisorption, TPR and TEM techniques. From XRD, the presence of hematite (Fe2O3) phase was detected in all precipitated iron catalysts and CFe2.5 phase in all used catalysts. TPR results showed that addition of Mg facilitated the reduction of Fe2O3 and decrease in reduction temperature. The catalytic performance was investigated in a fixed-bed reactor at 250 degrees C, 2 MPa pressure and H2/CO molar ratio of 2. Concentration of Mg was found to affect the CO conversion and product distribution. It was found that precipitated iron catalyst Fe/Mg/Cu/K with Mg/Fe ratio of 0.1 showed highest conversion (60.6%) and C5(+) selectivity (92.4%) among all catalysts tested.

Correlation between hydrogen bond basicity and acetylene solubility in room temperature ionic liquids.

Room temperature ionic liquids (RTILs) are proposed as the alternative solvents for the acetylene separation in ethylene generated from the naphtha cracking process. The solubility behavior of acetylene in RTILs was examined using a linear solvation energy relationship based on Kamlet-Taft solvent parameters including the hydrogen-bond acidity or donor ability (α), the hydrogen-bond basicity or acceptor ability (ß), and the polarity/polarizability (π*). It is found that the solubility of acetylene linearly correlates with ß value and is almost independent of α or π*. The solubility of acetylene in RTILs increases with increasing hydrogen-bond acceptor (HBA) ability of the anion, but is little affected by the nature of the cation. Quantum mechanical calculations demonstrate that the acidic proton of acetylene specifically forms hydrogen bond with a basic oxygen atom on the anion of a RTIL. On the other hand, although C-H···π interaction is plausible, all optimized structures indicate that the acidic protons on the cation do not specifically associate with the π cloud of acetylene. Thermodynamic analysis agrees well with the proposed correlation: the higher the ß value of a RTIL is, the more negative the enthalpy of acetylene absorption in the RTIL is.

Nano-sized cobalt based Fischer-Tropsch catalysts for gas-to-liquid process applications.

Nano-sized cobalt supported catalysts were prepared for Fischer-Tropsch synthesis in gas-to-liquid (GTL) process. The dependence of crystallite size and reducibility of Co3O4 on the supports were investigated with FTS activity. XRD peaks revealed nano crystallites (< 5.47 nm) of Co3O4 crystallites. TEM showed round shaped particles with size less than 5 nm. Support with higher acidity decreased crystallite size of Co3O4. XRD data of used catalysts showed Co3O4 crystallites smaller than 3.5 nm which do not reduce easily to Co(0) state. The crystallite size of Co3O4 plays a role in its reduction to Co(0). TPR results showed that the reduction temperature shifts to higher temperature due to metal-support interaction. The variation in the activity of the catalysts depends on the support which in turn affects the crystallite size, dispersion, reducibility and activity of Co species in Fischer-Tropsch Synthesis (FTS). In this study, Co/Al2O3 showed higher CO conversion than the other catalysts. However, the C5+ production was in order Co/SiO2 (78.1%) > Co/Al2O3 (70.0%) > Co/R_TiO2 (61%) > Co/A_TiO2 (57.5%).

Separation of olefin/paraffin mixtures using zwitterionic silver complexes as transport carriers.

Zwitterionic silver nitrate salts of 1-(1-methyl-3-imidazolio)propane-3-sulfonate, 1-(1-methyl-1-pyrrolidinio)propane-3-sulfonate, and 1-(4-methyl-4-morpholio)propane-3-sulfonate have been prepared and tested as carriers for facilitated olefin transport membranes in the separation of ethylene/ethane, propylene/propane, and C4 mixtures. The interactions of olefins with silver ions bound to sulfonate groups were investigated by FTIR spectroscopy as well as the correlation between the binding affinity of olefins and facilitated transport.

Stability of PEGylated salmon calcitonin in nasal mucosa.

The purpose of this study was to evaluate the stabilization of salmon calcitonin (sCT) by PEGylation in nasal mucosa. Degradation of native sCT in the homogenates of rat nasal mucosa was investigated by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The initial cleavage of sCT was due to tryptic-like endopeptidase activity, and the subsequent degradation followed the sequential pattern of aminopeptidase activity. To prepare PEGylated sCT resistant to the proteolytic degradation, the lysine residues susceptible to tryptic activity were selectively PEGylated by controlling reaction pH. The PEGylated sCT showed strong resistance against enzymatic degradation in rat nasal mucosa, with 56-fold prolonged half-life compared with that of native sCT. In the MALDI-TOF MS spectrum, the PEGylated sCT did not show any degradation peak for incubation of 120 min in the homogenates of rat nasal mucosa. The improved stability may be responsible for enhancing nasal absorption of PEGylated sCT.

Monitoring of peptide acylation inside degrading PLGA microspheres by capillary electrophoresis and MALDI-TOF mass spectrometry.

The purpose of this research was to assess the acylation reactions of peptides, salmon calcitonin (sCT), human parathyroid hormone 1-34 (hPTH1-34) and leuprolide, in poly(lactic-co-glycolic acid) (PLGA) microspheres. Capillary electrophoresis (CE) and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) were used for determining and monitoring peptide acylation and quantitating acylation products in the degrading PLGA microspheres. In the degrading PLGA microspheres of sCT and hPTH1-34, the acylation products were observed and determined to be adducts with glycolic acid units from degradable PLGA polymer by MALDI-TOF MS. In the microsphere of leuprolide, however, the acylation product was not observed even after 28 days of incubation at the release medium, which represents the different stabilities among peptides according to the primary structure. As the leuprolide contains tyrosine and serine having hydroxyl group of nucleophilic amino acids, the acylation reaction of peptide is shown to be mainly due to the primary amino groups of N-terminus or lysine residue. The complementary use of CE and MALDI-TOF MS will be useful for searching the counter measures as well as determining the peptide acylation in the manufactured formulations on the market.

New mechanistic insight into the coupling reactions of CO2 and epoxides in the presence of zinc complexes.

Coupling reactions of CO(2) and epoxide to produce cyclic carbonates were performed in the presence of a catalyst [L(2)ZnX(2)] (L=pyridine or substituted pyridine; X=Cl, Br, I), and the effects of pyridine and halide ligands on the catalytic activity were investigated. The catalysts with electron-donating substituents on pyridine ligands exhibit higher activity than those with unsubstituted pyridine ligands. On the other hand, the catalysts with electron-withdrawing substituents at the 2-position of the pyridine ligands show no activity; this demonstrates the importance of the basicity of the pyridine ligands. The catalytic activity of [L(2)ZnX(2)] was found to decrease with increasing electronegativity of the halide ligands. A series of highly active zinc complexes bridged by pyridinium alkoxy ions of the general formula [((mu-OCHRCH(2)L)ZnBr(2))(n)] (n=2 for R=CH(3); n=3 for R=H; L=pyridine or substituted pyridine) were synthesized and characterized by X-ray crystallography. The dinuclear zinc complexes obtained from propylene oxide adopt a square-planar geometry for the Zn(2)O(2) core with two bridging pyridinium propoxy ion ligands. Trinuclear zinc complexes prepared from ethylene oxide adopt a boat geometry for the Zn(3)O(3) core, in which three zinc and three oxygen atoms are arranged in an alternate fashion. These zinc complexes bridged by pyridinium alkoxy ions were also isolated from the coupling reactions of CO(2) and epoxides performed in the presence of [L(2)ZnBr(2)]. Rapid CO(2) insertion into the zincbond;oxygen bond of the zinc complexes bridged by pyridinium alkoxy ions leads to the formation of zinc carbonate species; these which yield cyclic carbonates and zinc complexes bridged by pyridinium alkoxy ions upon interaction with epoxides. The mechanistic pathways for the formation of active species and cyclic carbonates are discussed on the basis of results from structural and spectroscopic analyses.

Effect of chemical modification on the pharmacokinetics and biodistribution of carboxymethyl dextran as a drug carrier.

The in vivo fate of drugs conjugated to macromolecules inevitably depends on that of macromolecules. However, the in vivo fate of macromolecules also may be altered by conjugation to drugs. For the efficient design of carboxymethyldextran (CMD) conjugates of a new analgesic drug, DA5018, we investigated whether the chemical modifications alter the pharmacokinetics and tissue distribution of CMD itself. [(14)C]CMD, oxidized [(14)C]CMD ([(14)C]OCMD), [(14)C]OCMD conjugates of DA5018 ([(14)C]OCMD-DA5018) and [(14)C]OCMD conjugates of ethanolamine ([(14)C]OCMD-EA) were prepared and their molecular sizes were compared by size exclusion HPLC. The pharmacokinetics, biliary excretion, and tissue distribution of total radioactivity were compared after intravenous administration of each CMD derivative, 2.0 MBq/kg, to rats. The effective molecular sizes of CMD derivatives decreased in the order of [(14)C]CMD, [(14)C]OCMD-DA5018, [(14)C]OCMD, and [(14)C]OCMD-EA. After administration of each derivative, the mean AUC values of total radioactivity decreased with the decrease in the effective molecular size. The values of CL, Vss, and the amount of total radioactivity excreted in 24-hr urine increased considerably with the decrease in the effective molecular size. The tissue-to-plasma ratios of total radioactivity remaining in heart, liver, lung, kidney, and spleen at 24 hr also increased in the opposite order of the effective molecular size. Taken together, all these results demonstrate that the chemical modifications and physicochemical properties of attached chemicals can alter the pharmacokinetics and tissue distribution of CMD. One possible reason might be the difference in the effective molecular size of various CMD derivatives. Our study demonstrates that it may be necessary to consider the effect of chemical modification on the in vivo fate of macromolecules in designing macromolecular drug conjugates.