Perspectives on the reaction force constant

A synchronous, concerted chemical process is rigorously divided by the reaction force F(R), the negative gradient of V(R), into “reactant” and “product” regions which are dominated by structural changes and an intervening “transition” region which is electronically intensive. The reaction force constant κ(R), the second derivative of V(R), is negative throughout the transition region, not just at the nominal transition state, at which κ(R) has a minimum. This is consistent with experimental evidence that there is a transition region, not simply a specific point. We show graphically that significant nonsynchronicity in the process is associated with the development of a maximum of κ(R) in the transition region, which increases as the process becomes more nonsynchronous. (We speculate that for a nonconcerted process this maximum is actually positive.) Thus, κ(R) can serve as an indicator of the level of nonsynchronicity.

Mycopteris,a new neotropical genus of grammitid ferns (Polypodiaceae)

Mycopteris, a new genus of grammitid ferns, is described and combinations are made for the species that belong to it. Mycopteris is diagnosed by castaneous rhizome scales with turgid cells, usually pectinate laminae, blackish petioles and rachises, blackish pinna costae and veins, reddish setae, cretaceous hydathodes, glabrous sporangia, and the presence of Acrospermum ascomes. It is entirely neotropical, ranging from Mexico east into the West Indies and south to Bolivia. Mycopteris is one of two genera of grammitid ferns that are consistently associated with Acrospermum, an epibiotic ascomycete that produces black clavate fruiting bodies. Seventeen species of Mycopteris are recognized here, including one new species (M. longipilosa) and one elevated from the rank of variety to species (M. costaricensis). The following additional combinations are made here: M. alsopteris, M. amphidasyon, M. attenuatissima, M. cretata, M. grata, M. leucolepis, M. leucostica, M. longicaulis, M. pirrensis, M. praeceps, M. semihirsuta, M. steyermarkii, M. subtilis, M. taxifolia, and M. zeledoniana. Lectotypes are chosen for Ctenopteris leucosticta, Polypodium amphidasyon, and Polypodium pectinatum var. hispidum. For each accepted species, full synonymy and geographical range are provided. Taxonomic discussion is provided for species not widely recognized in previous treatments.     

New taxa and combinations in Malvastrum A. Gray (Malvaceae: Malveae)

The genusMalvastrum A. Gray is interpreted to include 22 taxa in 14 species. Seven taxa are here described as new, namely:M. americanum var.stellatum,M. tomentosum subsp.pautense,M. bicuspidatum subsp.campanulatum,M. bicuspidatum subsp.oaxacanum, M. bicuspidatum subsp.tumidum var.tumidum, M. bicuspidatum subsp.tumidum var.glabrum, andM. coromandelianum subsp.fryxellii. In addition, two new combinations are proposed, namely:M. tomentosum andM. coromandelianum subsp.capitato-spicatum.     

Taxonomy of Gundlachia (Compositae: Astereae)

Gundlachia, a genus of shrubs occurring in the Caribbean islands, is treated as comprising two species, one of which has six varieties. Five new combinations are made: Gundlachia corymbosa var. apiculata (Britton & S. F. Blake) M. A. Lane, G. corymbosa var. compacta (Urb. & Ekman) M. A. Lane, G. corymbosa var. cubana (Britton & S. F. Blake) M. A. Lane, G. corymbosa var. foliosa (Britton & S. F. Blake) M. A. Lane, and G. corymbosa var. ocoana (Urb. & Ekman) M. A. Lane. Gundlachia is probably most closely related to Gymnosperma.     

Two novel hydroperoxylated products of 20(S)-protopanaxadiol produced by Mucor racemosus and their cytotoxic activities against human prostate cancer cells

Microbial transformation of 20(S)-protopanaxadiol (1) by Mucor racemosus AS 3.205 yielded two novel hydroperoxylated metabolites and three known hydroxylated metabolites. The structures of the metabolites were identified as 26-hydroxyl-20(S)-protopanaxadiol (2), 23,24-en-25-hydroxyl-20(S)-protopanaxadiol (3), 25,26-en-24(R)-hydroperoxyl-20(S)-protopanaxadiol (4), 23,24-en-25-hydroperoxyl-20(S)-protopanaxadiol (5), and 25-hydroxyl-20(S)-protopanaxadiol (6). 4 and 5 are new compounds. Metabolites 2, 4, and 5 showed the more potent inhibitory effects against DU-145 and PC-3 cell lines than the substrate.     

Toward a census of genus Mimosa (Mimosaceae) in the Americas: a new species from Mexico (Baja California Sur) and two from planaltine Brazil (Goiás, Minas Gerais)

Three new species of Mimosa are described: M. (sect. Batocaulon) epitropica Barneby & León de la Luz from Mexico (Baja California Sur); and two from planaltine Brazil, M. (sect. Habbasia) bispiculata Barneby and M. (sect. Mimosa) demissa Barneby. The affinity of each is discussed, and all are illustrated.     

Four new diplostemonous species of mimosa (Mimosaceae) from Paraguay and eastern Bolivia

Four species of Mimosa, M. aureliana, M. chacoënsis, and M. tobatiensis known only from eastern Paraguay, and M. castanoclada known from northwestern Paraguay and eastern Bolivia, are described, figured, and compared with near kindred.     

Combination of 1,4-naphthoquinone with benzothiazoles had selective algicidal effects against harmful algae

A series of naphthoquinone-benzothiazole conjugates were synthesized as algicides, and their efficacies against harmful algal blooming species, such as Chattonella marina, Heterosigma akashiwo and Cochlodinium polykrikoides, were examined. The introduction of substituted benzothiazole at the C2 position of 1,4-naphthoquinone (compounds 1–9) resulted in higher algicidal activity against C. polykrikoides than the C6 conjugates (compounds 10–20). On the other hand, of the C6 conjugates, compounds 11 and 12 exhibited better algicidal activity against H. akashiwo, C. marina, and C. polykrikoides than the C2 conjugates. Further structure-activity analysis indicated that a replacement of the methoxy groups with hydroxyl groups (compounds 21–26) decreased the algicidal activity significantly. Among the various synthetic naphthoquinonebezothiazole conjugates tested, compound 12 was found to affect the most significant decrease in the level of C. polykrikoides growth, with an IC₅₀ of 0.19 μM. Compound 11 was found to be the most potent inhibitor against H. akashiwo and C. polykrikoides, with IC₅₀ values of 0.32 and 0.12 μM, respectively. Overall, these results highlight a possible method for controlling and inhibiting red tide forming algae using NQ derivatives.     

Dimeric bisbenzimidazoles: Cytotoxicity and effects on DNA methylation in normal and cancer human cells

Cancer cells are characterized by hypermethylation of the promoter regions of tumor suppressor genes. DNA methyltransferase inhibitors reactivate the genes, pointing to DNA methyltransferases as potential targets for anticancer therapy. Dimeric bisbenzimidazoles varying in the length of an oligomeric linker between two bisbenzimidazole residues (DB(n), where n is the number of methylene groups in the linker) were earlier shown to efficiently inhibit methylation of DNA duplexes by murine DNA methyltransferase Dnmt3a. Here, some of the compounds were tested for cytotoxicity, cell penetration, and effect on genomic DNA methylation in F-977 fetal lung fibroblasts and HeLa cervical cancer cells. Within the 0–60 μM concentration range, only DB(11) exerted a significant toxic effect on normal cells, whereas the effects of DB(n) on cancer cells were not significant. DB(1) and DB(3) slightly stimulated proliferation of HeLa and F-977 cells, respectively. DB(1) and DB(3) penetrated into the nuclei of HeLa and F-977 cells and accumulated predominantly in or near the nucleolus, while DB(11) was incapable of nuclear penetration. HeLa cells incubated with 26 μM DB(1) or DB(3) displayed a decrease in methylation of the 18S rRNA gene, which was in the regions of predominant accumulation of DB(1) and DB(3). The same DB(3) concentration exerted a similar effect on F-977 cells. However, the overall genomic DNA methylation level remained unchanged in both of the cell lines. The results indicated that DB(n)-type compounds can be used to demethylate certain genes and are thereby promising as potential anticancer agents.