Quantifying the Root-to-Shoot Transfer of 4,4'-Methylenedianiline Using Pressure Chamber and Intact Plant Methods.

The high-production-volume chemical 4,4'-methylenedianiline (4,4'-MDA) is an aromatic amine used to manufacture 4,4'-methylenedianiline diisocyanate for polyurethane production. Based on 4,4'-MDA's octanol/water partition coefficient (KOW ) and correlations with the transpiration stream concentration factor (TSCF), significant plant uptake and root-to-shoot transfer are predicted. However, most correlations between KOW and TSCF were developed for neutral organics and may not be applicable for ionizable bases such as 4,4'-MDA. To investigate, TSCF values for 4,4'-MDA were measured using pressure chamber and intact plant approaches for tomato, soybean, and wheat (intact plants only). 14 C-labeled 4,4'-MDA was used to increase analytical sensitivity and facilitate measurement of distribution within plant tissues. The TSCF of 14 C-MDA determined using the pressure chamber method was 0.04 ± 0.00 for tomato and 0.17 ± 0.10 for soybean. These values were lower than predicted from log KOW and within the range of values for 14 C-pyrene also measured in our study (0.14 ± 0.00 for tomato and 0.16 ± 0.09 for soybean). The TSCF values calculated from measurements made from intact plants grown to maturity were statistically equivalent to those obtained from the pressure chamber method for soybean and tomato. The distributions of 14 C within the three plants species were similar, with the roots > leaves ≈ stems > fruit. The log root concentration factors for 4,4'-MDA ranged from 3.68 to 4.33 for the three plant species. This finding indicates that the aromatic amine sorption to root materials is much greater than would be predicted based on its log KOW and may be the reason for the limited root-to-shoot transfer observed in the pressure chamber and intact plant studies. Environ Toxicol Chem 2023;42:655-662. © 2023 SETAC.

Comparison of Cortical Bone Fracture Patterns Under Compression Loading Using Finite Element-Discrete Element Numerical Modeling Approach and Destructive Testing.

Finite element analysis may not be the only method by which bone fracture initiation and propagation may be analyzed. This study compares fracture patterns generated from compression testing of bone to fracture patterns generated using a combination of both the finite element method (FEM) and discrete element method (DEM) as defined by the finite discrete element method (FDEM). Before testing, a three-dimensional bone model was developed using CT. Force and displacement data were collected during testing. The tested specimen was reimaged using CT. The solid model was discretized and material properties adjusted such that finite element-discrete element macro behavior matched the force-displacement data. A qualitative comparison of the fracture patterns demonstrates that FDEM can successfully be used to simulate and predict fracturing in bone, with this study representing the first time this has been done and reported.

Scalable and cost-effective tosylation-mediated synthesis of antifungal and fungal diagnostic 6″-Modified amphiphilic kanamycins.

Amphiphilic kanamycins bearing hydrophobic modifications at the 6″ position have attracted interest due to remarkable antibacterial-to-antifungal switches in bioactivity. In this report, we investigate a hurdle that hinders practical applications of these amphiphilic kanamycins: a cost-effective synthesis that allows the incorporation of various connecting functionalities to which the hydrophobic moieties are connected to the kanamycin core. A cost-effective tosylation enables various modifications at the 6″ position, which is scalable to a 90-g scale. The connecting functionalities, such as amine and thiol, were not the dominant factor for biological activity. Instead, the linear chain length played the decisive role. Amphiphilic kanamycin attached with tetradecyl (C14) or hexadecyl (C16) showed strong antifungal and modest antibacterial activities than with shorter chains (C6-C10). However, increases in chain length were closely correlated with an increase in HeLa cell toxicity. Thus, a compromise between the antimicrobial activities and cytotoxicities, for optimal efficacy of amphiphilic kanamycins may contain chain lengths between C8 and C12. Finally, the described synthetic protocol also allows the preparation of a fluorescent amphiphilic kanamycin selective toward fungi.

Experimental evolution and phenotypic plasticity of hindlimb bones in high-activity house mice.

Studies of rodents have shown that both forced and voluntary chronic exercise cause increased hindlimb bone diameter, mass, and strength. Among species of mammals, "cursoriality" is generally associated with longer limbs as well as relative lengthening of distal limb segments, resulting in an increased metatarsal/femur (MT/F) ratio. Indeed, we show that phylogenetic analyses of previously published data indicate a positive correlation between body mass-corrected home range area and both hindlimb length and MT/F in a sample of 19 species of Carnivora, although only the former is statistically significant in a multiple regression. Therefore, we used an experimental evolution approach to test for possible adaptive changes (in response to selective breeding and/or chronic exercise) in hindlimb bones of four replicate lines of house mice bred for high voluntary wheel running (S lines) for 21 generations and in four nonselected control (C) lines. We examined femur, tibiafibula, and longest metatarsal of males housed either with or without wheel access for 2 months beginning at 25-28 days of age. As expected from previous studies, mice from S lines ran more than C (primarily because the former ran faster) and were smaller in body size (both mass and length). Wheel access reduced body mass (but not length) of both S and C mice. Analysis of covariance (ANCOVA) revealed that body mass was a statistically significant predictor of all bone measures except MT/F ratio; therefore, all results reported are from ANCOVAs. Bone lengths were not significantly affected by either linetype (S vs. C) or wheel access. However, with body mass as a covariate, S mice had significantly thicker femora and tibiafibulae, and wheel access also significantly increased diameters. Mice from S lines also had heavier feet than C, and wheel access increased both foot and tibiafibula mass. Thus, the directions of evolutionary and phenotypic adaptation are generally consistent. Additionally, S-line individuals with the mini-muscle phenotype (homozygous for a Mendelian recessive allele that halves hindlimb muscle mass [Garland et al., 2002, Evolution 56:1,267-1,275]) exhibited significantly longer and thinner femora and tibiafibulae, with no difference in bone masses. Two results were considered surprising. First, no differences were found in the MT/F ratio (the classic indicator of cursoriality). Second, we did not find a significant interaction between linetype and wheel access for any trait, despite the higher running rate of S mice.