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NNadir

NNadir's Journal
NNadir's Journal
January 19, 2024

Discarded Face Masks and Effect on Marine Life.

The paper to which I'll refer in this post is this one: Identification of Additives in Disposable Face Masks and Evaluation of Their Toxicity Using Marine Medaka (Oryzias melastigma) Xiao-Pei Li, Guo-Yong Huang, Shu-Qing Qiu, Dong-Qiao Lei, Chen-Si Wang, Lingtian Xie, and Guang-Guo Ying Environmental Science & Technology 2024 58 (1), 121-131.

From the paper's introduction:

The outbreak of the COVID-19 has caused an enormous worldwide demand for face masks to mitigate airborne transmission of SARS-CoV-2. (1?3) It is estimated that ?200 million disposable plastic face masks are manufactured per day in June 2020 in China, which is the main supplier. (2) Meanwhile, more than 1 billion face masks are consumed globally each month in 2020. (1) As a result, about 1.4 billion face masks were casually discharged into the environment in March 2023 in China. (4) This improper disposal of face masks has led to their presence in aquatic environments (rivers and estuaries), ultimately contaminating the ocean ecosystem. (5?7) The discarded face masks have attracted public attention as a new pollution source of the marine environment. (8) However, there is a lack of data on the complete evaluation of the face mask pollution and their impact in marine wildlife. (1,2)

Face masks are typically manufactured using synthetic thermoplastic carbon polymers such as polypropylene (PP), polyethylene (PE), and polylactic acid (PLA). (2,6,9) Various organic additives, including plasticizers, flame retardants, dyes, etc., are supplemented in the polymers to enhance the properties of face masks. (10,11) These additives have been reported to be present in face masks. (10?12) For instance, up to 4.8 ?g/g di-n-butyl phthalate in face masks with 98.2% detection frequency (11) and 0.02 to 27.7 ?g/mask of organophosphate esters have been reported. (12) In addition, elevated levels of lithium (49.7 mg/g) and aluminum (6.2 mg/g) are found in face masks. (13) Nonetheless, the chemicals added in the face masks are far from fully understood due to the complexity of these additives.

The additives in the face masks can be leached out once they are in the ocean, posing a potential hazard to marine organisms. (2,6) Previous studies have demonstrated that plastic additives can cause various adverse effects on the development, nerve, and endocrine system in aquatic animals. (14?17) In addition, mask fragments can downregulate the transcription of target genes related to reproduction in zebrafish, (13) cause histopathological alterations of the liver, gills, and intestine of zebrafish, and disrupt their aggressive behavior. (18) However, research on the toxicity of face masks, particularly their additives, to marine organisms is extremely scarce.

In this study, one of the main objectives was to qualify and quantify the organic additives and metals in 13 face masks (biodegradable and nondegradable masks). The additives in face masks might be numerous and complex, necessitating the use of multiple biomarkers from different biological organizations to assess their toxicity. In addition, marine medaka (Oryzias melastigma) has been used as a marine fish model for the evaluation of the toxicity of pollutants. (19,20) Therefore, the potential toxicities of face masks (i.e., developmental toxicity, locomotor behavior, and estrogenic activity) using O. melastigma embryos and larvae were evaluated. The findings of this study will enable a better understanding of the risk face masks pose to marine ecosystem...


The results of the analysis of the face masks is shown graphically:



The caption:

Figure 2. Levels of organic additives (A) and metals (B) in face masks (FM). TeP: tris(2-ethylhexyl) phosphate; DiBP: diisobutyl phthalate; OM: octyl 4-methoxycinnamate; DEP: diethyl phthalate; TEP: triethyl phosphate; TPP: triphenyl phosphate; DHP: dihexyl phthalate; TbP: tris(2-butoxyethyl) phosphate; BBP: benzyl butyl phthalate; EDP: 2-ethylhexyl diphenyl phosphate.


The authors found that some of the substances listed changed the expression of 19 genes in the fish, and affected the swimming behavior of larval fishes.

There are likely human physiological effects of these additives as well as those observed in fish, but it is important to keep in mind that the risks posed by the face masks are more than likely far lower than the risks of getting Covid were or are.

In our society we seem to expect zero risks, but zero risks are impossible, always have been impossible, and always will be impossible. We seem to have, to steal and paraphrase a locution from the Poet Amiri Baraka, "...the single specious need to keep what we have never really had..."

Nevertheless, we should seek to minimize risks by at least hoping that what we believe to be "proper disposal" will in fact be proper disposal.

I was disturbed, during the height of Covid (when I was using a lot of masks myself) by seeing so many discarded as litter.

Have a nice weekend.

January 19, 2024

Weird Placement of "The Beginning."

On New Year's Eve Day, my family went to the Metropolitan Museum of Art.

It ended up that my sons went one way together; my wife and I another, and eventually, while we were in the Degas/Monet exhibition, my wife and I ended up split, so I wandered the Museum on my own.

I had tried to convince my family before choosing the Met to try the Neue Museum, which focuses on Early 20th Century German art, notably Gustav Klimt (who was in fact, not German, but Austrian) because they were having a show dedicated to an artist whose work speaks profoundly to me, Max Beckmann, but I was outvoted, 3-1.

Max Beckmann, the Formative Years at the Neue Gallery.

(In defense of my family, they have agreed on multiple occasions to go to Max Beckmann shows, and one of my happiest memories is coming across his Departure at the Modern when he was in Art School. (Internet renditions of this painting do not capture its enormity; he painted this powerfully disturbing painting just after Hitler came to power in Germany, declaring his work "Degenerate Art." )

Well, the consolation for losing the vote is that The Met has one of Beckmann's greatest Paintings (my favorite though, being Departure), the triptych "The Beginning:"



(This painting is also not captured by internet renditions, like Departure, it cannot be captured on the internet, because like Departure it is a very large painting.)

I came across it in my wanderings, but it was in a weird place, among medieval triptychs, which were largely devoted to religious subjects, and totally divorced from Beckmann's culture.

The only relationship between this medieval religious art and Beckmann's painting is that they are triptychs. I suppose Beckmann had his reasons for choosing this format, and it is true that he died on the sidewalk beside Central Park on the way to see his first show at the Met, and so his relationship with the Met has special significance, but, I don't know, it struck me as weird.

In fact, I couldn't look at any of the other paintings in the room when I was in the room; the only medieval religious triptychs that interest me are those by Hironimus Bosch, most notably The Garden of Earthly Delights.

I'm not sure why The Met put Beckmann where they did, but it certainly struck me as a cultural clash, which was, perhaps, what the Curator had in mind.

January 19, 2024

Global survey finds high public support for nuclear

Before linking the article, I would like to note that public attitudes do not necessarily correspond to wisdom. If this poll produced the result that the general public was hostile to nuclear energy, as it has been at times, nuclear energy would still be the only sustainable and reliable form of energy there is. Opposition to nuclear energy kills people by resulting in air pollution and climate change.

In addition, I have no idea about the validity of this poll or whether it was a "push" poll, nonetheless, the results are promising if valid although it is too late for nuclear energy to save what might have been saved were it not for antinuclear public attitudes.

Global survey finds high public support for nuclear

Subtitle:

One-and-a-half times more people support the use of nuclear energy than oppose it, according to a multinational public opinion poll conducted by market research firm Savanta on behalf of energy consultancy Radiant Energy Group.


The Public Attitudes toward Clean Energy (PACE) index is described as "the world's largest publicly-released international study on what people think about nuclear energy", with data collected from more than 20,000 respondents from 20 countries.

"The PACE index was set up to track support/opposition for clean energy sources, what drives those attitudes, and how institutions can better cater to what the public wants," Radiant Energy said.

The survey found that, across the 20 countries surveyed, 28% of respondents oppose the use of nuclear energy while 46% support it. Of the 20 countries surveyed, 17 have net support for nuclear energy's use. Support was found to be more than three times higher than opposition in the world's two most populated countries, China and India.

Preference for nuclear energy was found to be larger than for onshore wind, biomass from trees, or gas with carbon capture and storage. Twenty five percent of those surveyed said their country should focus on nuclear energy, behind only the 33% preference for large-scale solar farms.

Nuclear is seen as the most reliable thermal source of energy, with 66% of respondents saying nuclear is reliable. The survey found that people who view nuclear energy as reliable have over four times more support for its use.

However more than half (53%) of respondents thought nuclear energy created a fair amount or a great deal of greenhouse gas emissions...


The last sentence above reflects public stupidity.

Another excerpt:

...Within nuclear-powered countries, more than three times more respondents want to keep using nuclear power than phase it out. Within the four countries without existing commercial reactors, twice as many respondents want to construct new nuclear power plants rather than ban their use.

"This year may have marked a turning point for the nuclear energy industry," said Richard Ollington, Partner at Radiant Energy. "The COP28 pledge to triple global nuclear capacity by 2050 meets the public’s overwhelming demand for new nuclear to be built. The nuclear industry, as well as the governments and banks that support it, should carefully listen to what the public wants and start delivering beyond what the public expects..."


It seems that my son's decision to go into nuclear engineering was a wise one. I try to emphasize to him that his task and the task of his colleagues is very serious, to save the world.

This may come under the general rubric of "too little, too late," but the second best time to embrace nuclear energy is now. The best time was 30 or 40 years ago.
January 19, 2024

The Response of Human Immune Cells to PFAS Pollution, Intractable Per and Poly Fluoralkylate Substances

The paper to which I will refer is this one: Altered Transcriptome Response in PBMCs of Czech Adults Linked to Multiple PFAS Exposure: B Cell Development as a Target of PFAS Immunotoxicity Barbora Rudzanová, Vojtěch Thon, Hana Vespalcová, Christopher J. Martyniuk, Pavel Piler, Martin Zvonař, Jana Klánová, Luděk Bláha, and Ondrej Adamovsky Environmental Science & Technology 2024 58 (1), 90-98.

The paper is open access; anyone can read it. It is however, fairly technical. Although my own work with the molecular biology of PBMC's, (peripheral blood mononuclear cells) has been limited, and was somewhat peripheral as opposed to "hands on" - it concerned the alkylation of histones, the proteins that wrap and orchestrate the expression of DNA, modifications of which are involved in cancer, primarily acetylation - I can briefly indicate that "PBMC's are white blood cells that help orchestrate immune response. When they are dysfunctional, leukemia is one result. I will briefly excerpt the portions below that do not require too much scientific sophistication.

The authors of this paper have previously explored the relationship of PFAS contamination in citizens of the Czech Republic and association with immunologically moderated disease states: Barbora Rudzanova, Jelle Vlaanderen, Jiří Kalina, Pavel Piler, Martin Zvonar, Jana Klanova, Ludek Blaha, Ondrej Adamovsky, Impact of PFAS exposure on prevalence of immune-mediated diseases in adults in the Czech Republic, Environmental Research, Volume 229, 2023, 115969.

Excerpts from the introduction:

Per- and polyfluoroalkyl substances (PFASs) are emerging environmental contaminants that have been used since the 1940s. PFASs, due to their surfactant properties and chemical stability, have found many applications in industry as well as in the consumer sector. (1) Due to their high stability, PFASs persist in the environment and thus can be found in water, soil, and air. Therefore, people and other living organisms are continuously exposed to these chemicals. (2) Alarmingly, PFASs have been found in human matrices with high frequency. The United States of America (U.S.A.) and European epidemiological and biomonitoring studies report that PFASs are present in human blood, often with a detection frequency above 90%. (3,4)

PFAS exposure has been associated with adverse health outcomes, such as liver damage, endocrine disruption, liver and testicular cancer, and immune disruption. (5) Suppressed antibody response after vaccination is one of the frequently described effects of the immune disruption associated with PFASs. (6,7) Further, PFAS exposure has been associated with an increased risk of infectious diseases, the prevalence of asthma, and altered immunological responses in allergies. (7) Taken together, it is evident that PFASs are immunomodulatory stressors; however, the mechanism of action has still not been fully elucidated, specifically in humans.

A number of epidemiological studies have indicated that PFASs interfere with antibody production. Experimental studies reviewed recently by Ehrlich et al. in 2023 suggest the involvement of nuclear receptors, such as NF-?B and PPARs, and/or calcium signaling. (8) Data from both epidemiological and toxicological studies are valuable for determining adverse outcome pathways (AOPs), i.e., the set of casually linked events leading from the initial molecular event to the apical health effect. Especially, the identification and quantification of biomarkers of effect provide valuable data for building AOPs. (9) By implementing omics and advanced bioinformatics, biomarkers of effect on biological levels such as the genome, transcriptome, proteome, and metabolome can be revealed. These omics technologies are useful for characterizing the effect of PFASs on human health and, most importantly, revealing an early event that may lead to adverse health effects. (10,11) Genome-wide transcriptomic analysis of immune blood cells, for example, can uncover valuable information about complex immune signaling. This technique allows researchers to analyze the complete set of ribonucleic acid (RNA) transcripts present in cells, providing valuable insights into the gene expression patterns underlying immune responses...

...the objective of this study was to identify a transcriptomic response that is conserved for multiple PFASs, including the seven most abundant ones: perfluoropentanoate (PFPA), perfluorooctanoate (PFOA), perfluorononanoate (PFNA), perfluorodecanoate (PFDA), perfluoroundecanoate (PFUnDA), pefluorohexanesulfonate (PFHxS), and perfluorooctanesulfonate (PFOS). To reach this aim, the gene expression profiles within human immune cells in relation to PFAS blood levels from a cross-sectional Czech adult cohort study were researched. Using this approach, we aimed to uncover the molecular responses underlying PFAS-associated immunomodulation in humans. Through the utilization of transcriptomics, our research endeavors shed light on the specific gene expression patterns, molecular pathways, and regulatory mechanisms involved in the immune system’s response to PFAS exposure.


A very brief excerpt from the conclusion of the paper:

Taken together, the results of the current study indicate that multiple PFAS exposure influences the immune system in the phase of late B cell development, specifically B cell activation, GC reactions, and plasma cell development. As GCs and plasma cells are essential for antibody production, the findings of the current study are in line with suppressed antibody responses after vaccination associated with PFAS exposure, which has been largely reported in the literature. (6,56?60)


Yes but, you have to admit, Scotch Guard did prevent stains on the furniture.

It is possible to destroy PFAS with exposure to high energy radiation, but this technique is not readily exploited, and in any case, it is difficult to process ubitiquous contaminants.

I trust you will enjoy the upcoming weekend.
January 17, 2024

Highest ever daily average CO2 concentration recorded at the Mauna Loa CO2 observatory.

Here you go folks:

January 15: 422.36 ppm
January 14: 422.85 ppm
January 13: 424.96 ppm
January 12: Unavailable
January 11: 422.78 ppm
Last Updated: January 16, 2024

Recent Daily Average Mauna Loa CO2

Out of 15,256 readings, which can be found at the Observatory's data page, extending back to May 17, 1974, almost 50 years ago, 424.96 ppm is the highest ever recorded. More telling it is the only such reading of the 40 that exceeded 424 ppm that didn't take place in 2023.

We're off to a great start in 2024, aren't we?

I know, I know, I know, solar wind, "zillion percent" "by 2050" or "by 2040" "by 2060" or "by whenever", electric cars...

I don't know who we think we're kidding, but some of us are clearly kidding ourselves, but as kidding goes, it's not even remotely funny.

I trust you're having a nice day, and if you are driving in the Northeast, that you are safe.

January 16, 2024

Moltex Issued Canadian Patent for Molten Salt Nuclear Fuel Reprocessing,.

Some brief comments below.

[link:Moltex recycling process granted Canadian patent|Moltex recycling process granted Canadian patent]

Subtitle:

The patent covers Moltex Energy Canada's Waste To Stable Salt (WATSS) process for converting any uranium oxide fuel into molten salt reactor fuel, part of a suite of technologies being developed by the company alongside its Stable Salt Reactor - Wasteburner (SSR-W) fast reactor and GridReserve thermal energy storage system.


Brief excerpt:

The process was invented by Ian Scott, Moltex's co-founder and chief scientist. It involves the conversion of used nuclear fuel into products and by-products:.. transuranics, along with some uranium and fission products, are extracted into a salt which forms the fuel for the SSR-W reactor and some other reactors; uranium - a major by-product - which is considered as intermediate to low level radioactive waste, but can also have other uses; and fission products, a byproduct which can be disposed directly or used as a heat source for remote applications.

Unlike conventional reprocessing routes, the WATSS process is unable to produce pure plutonium which could be misused for "nefarious purposes", the company said. As well as removing this proliferation risk, this also makes it simpler and less expensive than conventional reprocessing, it added...


I haven't studied this company in any detail, but if memory serves me well, they're a chloride salt company. I generally have reservations about chloride salts.

All of my main own ideas around fuel reprocessing are connected with molten salt/pyroprocessing/electrorefining/distillation, which may or may not be significantly different than their approach. I favor technologies that can produce chemically pure plutonium, for a number of reasons on which I won't expand here, but the most beautiful part of what Moltex is promoting is to put the fission products to use, which in fact, have many uses beyond heat sources for remote applications.

All of the components of used nuclear fuel, properly regarded, are potentially extremely valuable.

These kind of innovations, if not impeded by mysticism, fear, ignorance, and reactionary thinking, are a path to building a sustainable world. Whether we do that, build a sustainable world, is an open question, frankly not looking good, but this kind of tech makes it possible to consider a sustainable world as at least being possible.

Have a nice day tomorrow.

January 15, 2024

Nora Zakaria Paves Her Own Path in Waste Management

IAEA Profile: Nora Zakaria Paves Her Own Path in Waste Management

Nora Zakaria comes from a humble background. At eight years old, in her home country of Malaysia, she would wake up before dawn to go rubber tapping to harvest latex with her mother and sister. With mosquito repellent coils placed on their heads, she complained about the tedious work to which her mother responded, “Study hard if you do not want to work like this.”

Zakaria took her mother’s advice to heart and prioritized her studies. At university, although she planned to study chemistry, she switched her major when the Government of Malaysia offered her a full scholarship to study chemical engineering in the United Kingdom.

Chemical engineering was not her first choice, but she took the opportunity, which opened the door to the world of nuclear energy and radioactive waste management. Her studies set her on course for a career that would eventually lead to her current role as Head of the Waste Technology Section at the IAEA...

...Zakaria started her career as a Research Officer at the Malaysian Nuclear Agency (MNA) nearly 20 years ago. Over the past two decades, she was more drawn to the topic of radioactive waste management. At the MNA, she revamped the Waste Management Centre and rose to the challenges of undertaking radioactive waste management in Malaysia...

...Since joining the IAEA as Head of the Waste Technology Section, she has applied her knowledge gained from previous experiences to tackle challenges faced by IAEA Member States with radioactive waste management programmes...


?itok=BPoLk9AP
January 14, 2024

Discovery of Enzymes to Catalyze Pericyclic Reactions.

A couple of days ago I attended a lecture by K.N. Houk which inspired me to look into a subject about which I have not thought for a long time, my days in synthetic chemistry being far behind me; somehow I drifted elsewhere. As a result, partly out of nostalgia, partly out of curiosity, a partly because of my disappointed realization that I could have been, should have been, more, I was inspired to check out this paper pointing to a topic about which I'd only mused casually, this many years ago: Masao Ohashi, Fang Liu, Yang Hai, Mengbin Chen, Man-cheng Tang, Zhongyue Yang, Michio Sato, Kenji Watanabe, K. N. Houk & Yi Tang, SAM-dependent enzyme-catalysed pericyclic reactions in natural product biosynthesis. Nature 549, 502–506 (2017).

The question is that while pericyclic reactions - reactions that feature, in the thermal case, 2n + 2 electrons moving in a quasi aromatic transition state (i.e., 2, 6, 10, 12...electrons, most commonly 6) in such a way that the stereochemistry is tightly controlled - are frequently used in laboratory syntheses of complex natural products, in nature, these types of reactions are not particularly well characterized in biological systems. I sort of mused about this in a half serious way; it never occurred to me to seriously look into the matter. In fact, I never even thought as to whether biological pericyclic reactions were common or even known.

It turns out they are known.

The abstract of the paper points, quite well, to the question I never more than casually asked myself:

Pericyclic reactions—which proceed in a concerted fashion through a cyclic transition state—are among the most powerful synthetic transformations used to make multiple regioselective and stereoselective carbon–carbon bonds1. They have been widely applied to the synthesis of biologically active complex natural products containing contiguous stereogenic carbon centres2,3,4,5,6. Despite the prominence of pericyclic reactions in total synthesis, only three naturally existing enzymatic examples (the intramolecular Diels–Alder reaction7, and the Cope8 and the Claisen rearrangements9) have been characterized. Here we report a versatile S-adenosyl-L-methionine (SAM)-dependent enzyme, LepI, that can catalyse stereoselective dehydration followed by three pericyclic transformations: intramolecular Diels–Alder and hetero-Diels–Alder reactions via a single ambimodal transition state, and a retro-Claisen rearrangement. Together, these transformations lead to the formation of the dihydropyran core of the fungal natural product, leporin10.


From the paper's introduction:

Naturally existing enzymatic pericyclic reactions are rare12,13,14. Indeed, only a handful of enzymes that can catalyse these reactions have been characterized over the past five decades (Fig. 1a)7,8,9,12,13,14, even though pericyclic reactions have been proposed as key transformations in the biosynthesis of many polycyclic natural products12,15,16. We sought an enzyme-catalysed inverse electron demand hetero-Diels–Alder (HDA) reaction17 that constructs heterocycles in natural products (Fig. 1a). The HDA reaction has been proposed as a key biotransformation yielding dihydropyran cores, which are prevalent structural features in natural products that include the cytotoxic leporin B (1) from Aspergillus species (Fig. 1b)10,15,16,18. The biomimetic synthesis of the dihydropyran core in leporin uses the E/Z geometric mixture of the unstable ?-quinone methide19 intermediate 5 generated from the dehydration of alcohol 4. The uncatalysed process gives a mixture of the minor desired HDA adduct leporin C (2) and major other regio- and stereoisomeric intramolecular Diels–Alder (IMDA) and HDA adducts (Fig. 1c)20. It was therefore proposed that an enzyme must be encoded in the biosynthetic pathway of leporins to catalyse the HDA cycloaddition in a stereoselective fashion and to suppress the IMDA reaction to afford the dihydropyran core in 2 (Fig. 1c)14.


A figure:



The caption:

a, Examples (ex) of pericyclic reactions and enzymes that can catalyse pericyclic reactions. Known and unknown enzymatic reactions are shown in black and grey arrows, respectively. EDG, electron donating group; EWG, electron withdrawing group; HOMO, highest occupied molecular orbital; LUMO, lowest unoccupied molecular orbital; b, The structures of natural products containing dihydropyran, which would be biosynthesized by HDA reaction. Variecolortide A is naturally racemic; the relative stereochemistry of epipyridone and leporin B are shown. c, The putative leporin biosynthetic gene cluster in A. flavus and the assignment of encoded genes and biosynthetic pathway of leporins. PKS–NRPS, polyketide synthase–non-ribosomal peptide synthetase; TF, transcription factor; MCT, monocarboxylate transporter; SDR, short-chain dehydrogenase/reductase; ER, enoylreductase; OMT, O-methyltransferase. The structures show the relative stereochemistry. d, Analysis of metabolites from the transformants of A. nidulans by HPLC. The peak at 12?min corresponds to the tetramic acid product that is biosynthesized by LepA (PKS–NRPS) and LepG (ER).


Some more text:

The biosynthetic gene cluster of leporin B (1) in Aspergillus flavus has been reported and genetically verified (Fig. 1c)10. However, no clear enzyme candidate that can catalyse the pericyclic reaction was apparent in the cluster. To identify the enzyme responsible for this biotransformation, we heterologously reconstituted the leporin B (1) biosynthetic pathway in Aspergillus nidulans (Fig. 1c, d)21. As shown in Fig. 1d, coexpression of the polyketide synthase?non-ribosomal peptide synthetase (PKS?NRPS) LepA, the partnering enoyl reductase (ER) LepG, and the ring-expansion P45022 LepH led to the biosynthesis of the ketone 3. Additional coexpression with the short chain dehydrogenase/reductase (SDR) LepF, which is hypothesized to reduce 3 to the alcohol 4, led to a mixture of HDA products including the desired dihydropyran 2 as a minor product and the diastereomer 9, as well as the spirocyclic IMDA products 6–8 (Fig. 1c, d). Among these products, 2 and 6 are proposed to be derived from the quinone methide (E)-5, while 7–9 are from (Z)-5 (Fig. 1c). These results are consistent with biomimetic synthetic observations, and indicate that in order to biosynthesize 2 as the desired pericyclic reaction product, enzymatic stereocontrol of dehydration of 4 to (E)-5, as well as control of the subsequent pericyclic reaction, are required.

The only remaining annotated enzyme in the gene cluster is LepI, which is predicted to be an O-methyltransferase (OMT) with a well-conserved SAM binding site even though no O-methylation step is required for leporin B (1) biosynthesis. When lepI was introduced into the A. nidulans strain that produced the various pericyclic products derived from reduction of 3, we were surprised to observe the exclusive production of 2 without any other products (Fig. 1d). Further addition of the P450 lepD yielded the final product 1, thereby completing heterologous pathway reconstitution (Fig. 1c, d). To first verify the function of SDR LepF, recombinant protein was expressed from Saccharomyces cerevisiae and assayed in the presence of 3 and NADPH, which yielded a single product 4 corresponding to the reduced compound (Extended Data Fig. 1). To obtain sufficient 4 for assay with LepI, we reduced 3 with NaBH4 which gave both 4 and diastereomer 4? in a ratio of approximately 1:1 (Extended Data Figs 1, 2). Each isomer was isolated and immediately added to LepI expressed and purified from Escherichia coli. Both 4 and 4? dehydrated spontaneously in the absence of LepI and afforded a mixture of IMDA (6–8) and HDA (2 and 9) products, with 2 being a very minor product (Fig. 2a). However, when LepI was added to 4, complete conversion to 2 was accomplished in the absence of any added cofactors (Fig. 2a). In contrast, addition of LepI to 4? had only a small effect on product profile. The collective in vivo and in vitro data therefore point to LepI being solely responsible for formation of 2 starting from 4, which requires stereoselective dehydration to yield (E)-5 and subsequent HDA reaction to 2...


"SAM" is a nucleoside, adenosine, that has alkylated a methionine, "S-adenosyl methionine," a sulfonium ion. It is a moiety that is often found in biosynthetic methylations. Methionine itself is one of the 20 coded amino acids.

This paper is highly cited. A description of the mechanism and the nature of the SAM cofactor's role in the mechanism can be found here: Min Chang, Yu Zhou, Hao Wang, Zihe Liu, Yi Zhang, Yue Feng, Crystal structure of the multifunctional SAM-dependent enzyme LepI provides insights into its catalytic mechanism, Biochemical and Biophysical Research Communications, Volume 515, Issue 2, 2019, Pages 255-260, and probably elsewhere.

This is a little esoteric, but it made me think a lot outside of the little box in which I live and to reflect a bit on my life and despite much happiness, some regrets.

January 14, 2024

The IEAE Praises Kenya's Progress in Building Nuclear Infrastructure

IAEA sees 'significant progress' in Kenya's research reactor preparations

Subtitle:

Kenya is pursuing the development of the country's first research reactor, a stepping stone towards a future nuclear power programme, and invited an International Atomic Energy Agency (IAEA) mission to review the development of its national nuclear infrastructure.


A brief excerpt of the brief article:

Andrey Sitnikov, who led the Integrated Nuclear Infrastructure Review for Research Reactors Mission and is the technical lead of the IAEA Research Reactor Section, said: "Kenya has demonstrated a sustained and very professional approach to the development of its research reactor programme. We noted that before making the final decision, Kenya did a great job of developing and preparing laws and regulatory documents, actively involving interested stakeholders in the programme, and developing human resources of both the future operator and the regulator."

The eight-member mission team, from India and the USA and six IAEA staff members, conducted the nine-day mission in December, reviewing the status of the country's nuclear infrastructure development against the Phase 1 criteria from the IAEA's Milestones Approach, which provides guidance for the preparation of a research reactor project on 19 issues ranging from nuclear safety and waste managements to financing.

The mission team provide recommendations and suggestions for the further development of nuclear infrastructure. Kenya plans to commission its first research reactor in the early 2030s. In September 2023 the Nuclear Power and Energy Agency (NuPEA) announced a potential project for a 1000 MWe nuclear plant located in either Kilifi or Kwale...


Have a nice day.
January 14, 2024

At the Mauna Loa CO2 Observatory, 2024 Starts With a Fairly Disgusting Bang.

As I've indicated repeatedly in my DU writings, somewhat obsessively I keep a spreadsheet of the weekly data at the Mauna Loa Carbon Dioxide Observatory, which I use to do calculations to record the dying of our atmosphere, a triumph of fear, dogma and ignorance that did not have to be, but nonetheless is, a fact.

Facts matter.

When writing these depressing repeating posts about new records being set, reminiscent, over the years, to the ticking of a clock at a deathwatch, I often repeat some of the language from a previous post on this awful series, as I am doing here with some modifications. It saves time.

As I've been reporting over the years in various contexts, the concentrations of the dangerous fossil fuel waste carbon dioxide which is killing the planet fluctuate sinusoidally over the year, with the rough sine wave superimposed on a quadratic axis:



Monthly Average Mauna Loa CO2

January 1-6 were part of week 52, beginning on 12/31/2003. Here's the data for the first full week on 2024, Week 1:

Week beginning on January 07, 2024: 423.47 ppm
Weekly value from 1 year ago: 419.54 ppm
Weekly value from 10 years ago: 398.26 ppm
Last updated: January 13, 2024


Weekly average CO2 at Mauna Loa (Accessed 01/14/2024)

2024's first full week shows an increase over week 1 of 2023 of 3.93 ppm in the concentration of the dangerous fossil fuel waste CO2.

As of this writing, 2502 weekly data points are recorded at the Mauna Loa website, and can be accessed from the data pages. The current reading is the 22nd highest. Of the 50 highest, 13 have taken place in the last 5 years, 33 in the last 10 years, and 40 in this century. Of the 10 that occurred in the 20th century, six occurred in 1998 when the rain forests in S.E. Asia caught fire after slash and burn fires set to make palm oil plantations for "renewable biodiesel" for Germany went out of control.

The comparator with the value 10 years ago is 25.21 ppm higher than that of the first week of 2014. Of the 50 highest 10 year comparators, this is 23rd highest, out of 2046 pieces of such data. All of the top 50 in this category have taken place since 2019.

There are people here who believe that the reactionary return to 19th century dependence on the weather for energy supplies - abandoned for a reason - is about addressing climate change.

This has never been true. Enthusiasm for so called "renewable energy" was originally not about addressing climate change, for which it is clearly inadequate. It's clearly not working and never had a chance of doing so. The land and material intensity of so called "renewable energy" are unsustainable.

Things are getting worse faster than ever.

Enthusiasm for so called "renewable energy" was always about attacking the only sustainable scalable form carbon minimized clean energy, nuclear energy. In this, it was successful, arresting progress in nuclear energy in its tracks by popularizing bad thinking, selective attention and by sweeping the consequences of this anti-progressive scheme to entrench fossil fuels under the rug by diverting attention from it.

The antinuke scheme of ignoring fossil fuels, the death toll, the environmental destruction, and collapse of the atmosphere, is unraveling; nuclear energy is no longer a pariah. Almost certainly it's too little, too late. The planet is burning.

Have a nice Sunday afternoon.

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