Sulfur is an element necessary for the life cycle of higher plants. Its assimilation and reduction into essential biomolecules are pivotal factors determining a plant’s growth and vigor as well as resistance to environmental stress. While certain soil microbes can enhance ion solubility via chelating agents or oxidation, microbial regulation of plant-sulfur assimilation has not been reported. With an increasing understanding that soil microbes can activate growth and stress tolerance in plants via chemical signaling, the question arises as to whether such beneficial bacteria also regulate sulfur assimilation. Here we report a previously unidentified mechanism by which the growth-promoting rhizobacterium Bacillus amyloliquefaciens (GB03) transcriptionally activates genes responsible for sulfur assimilation, increasing sulfur uptake and accumulation in Arabidopsis. Transcripts encoding for sulfur-rich aliphatic and indolic glucosinolates are also GB03 induced. As a result, GB03-exposed plants with elevated glucosinolates exhibit greater protection against the generalist herbivore, Spodoptera exigua (beet armyworm, BAW). In contrast, a previously characterized glucosinolate mutant compromised in the production of both aliphatic and indolic glucosinolates is also compromised in terms of GB03-induced protection against insect herbivory. As with in vitro studies, soil-grown plants show enhanced glucosinolate accumulation and protection against BAW feeding with GB03 exposure. These results demonstrate the potential of microbes to enhance plant sulfur assimilation and emphasize the sophisticated integration of microbial signaling in plant defense.

Novel proton di-ionizable p-tert-butylcalix[4]arene-crown-6 compounds in cone, partial-cone and 1,3-alternate conformations are synthesized to compare the efficiency and selectivity with which they extract alkaline earth metal ions. In these ligands, a crown-6 polyether unit links alternate aromatic rings of the calix[4]arene framework. To the remaining lower-rim positions are attached oxyacetic acid or N-(X)sulfonyl oxyacetamide groups. Changing the conformation varies the spatial relationship between a polyether-complexed divalent metal ion and the ionized side arms of the ligands. This is found to markedly affect the efficiency and selectivity in competitive solvent extraction of alkaline earth metal ions from aqueous solutions into chloroform by the di-ionizable calix[4]arene-crown-6 ligands.

3D chirality of sandwich type of organic molecules has been discovered. The key element of this chirality is characterized by three layers of structures that are arranged nearly in parallel fashion with one on top and one down from the center plane. Individual enantiomers of these molecules have been fully characterized by spectroscopies with their enantiomeric purity measured by chiral HPLC. The absolute configuration was unambiguously assigned by X-ray diffraction analysis. This is the first multilayer 3D chirality reported and is anticipated to lead to a new research area of asymmetric synthesis and catalysis and to have a broad impact on chemical, medicinal, and material sciences in future.

Capillary electrophoresis (CE) is now clearly the separation technique of the decade. One aspect that is still in need of improvement is concentration sensitivity, especially when CE is used in conjunction with on-column UV-visible absorptiometry, by far the most common practice. Electromigration injection (EI) is among the most prominent techniques in CE that serves to improve the attainable limits of detection; it is also the most convenient and simplest of all injection modes. Unfortunately, EI is affected both from sample to sample (the amount of an analyte introduced depends on sample conductance) and from analyte to analyte within a sample (the introduction is strongly biased on analyte electrical mobility). Previously we have shown the utility of small loops affixed at the tip of a capillary (Anal. Chem. 1995, 67, 3853-3860; 1996, 68, 1164-1168). The present paper shows that there are remarkable advantages to be gained from forming a film of the sample solution on a wire loop and using the loop itself as the high-voltage electrode to perform electromigration from a very small sample volume. The sample constituents can be essentially exhaustively electromigrated from this volume in less than 1 min, and the mobility induced bias is dramatically lowered. The observed experimental behavior agrees with theoretical models.

Little is known about the optimal time to consume caffeine prior to exercise to maximize the ergogenic benefits of the substance.Purpose: To determine the optimal pre-exercise time interval to consume caffeine to improve lower-body muscular performance. A secondary aim was to identify the presence of any sex differences in responses to timed caffeine administration.Methods: Healthy, resistance-trained males (n = 18; Mean±SD; Age: 25.1 ± 5.7 years; Height: 178.4 ± 7.1 cm; Body mass: 91.3 ± 13.5 kg; Percent body fat: 20.7 ± 5.2; Average caffeine consumption: 146.6 ± 100.3 mg/day) and females (n = 11; Mean ± SD; Age: 20.1 ± 1.6 years; Height: 165.0 ± 8.8 cm; Body mass: 65.8 ± 10.0 kg; Percent bodyfat: 25.8 ± 4.2; Average caffeine consumption: 111.8 ± 91.7 mg/day) participated in this investigation. In a randomized, double-blind, placebo-controlled, crossover fashion, participants consumed 6 mg·kg−1 caffeine or placebo solution at three time points: 2 h prior (2H), 1 h prior (1H), or 30 min prior (30M) to exercise testing. During three visits, caffeine was randomly administered at one time point, and placebo was administered at the other two time points. During one visit, placebo was administered at all three time points. Next, participants performed isometric mid-thigh pulls (IMTP), countermovement vertical jumps (CMVJ), and isometric/isokinetic knee extensor testing (ISO/ISOK).Results: Caffeine administered at 1H significantly improved absolute CMVJ and ISO performance relative to placebo. Mean CMVJ jump height was significantly higher during 1H compared to 30M. However, only caffeine administered at 30M significantly improved absolute measures of isokinetic performance. Analysis of the pooled caffeine conditions revealed that muscular performance was more consistently augmented by caffeine in males compared to females.Conclusions: Pre-exercise caffeine timing significantly modulated participant responses to the substance, with 1H exerting the most consistent ergogenic benefits relative to other time points, particularly compared to 2H. Male participants were found to respond more consistently to caffeine compared to female participants. These results suggest that active individuals can maximize the ergogenic effects of caffeine by consuming the substance ~1 h prior to the point when peak muscular performance is desired.