Untargeted metabolomic analysis reveals a potential role of saponins in the partial resistance of pea (Pisum sativum) against a root rot pathogen, Aphanomyces euteiches.

In soil-borne diseases, the plant-pathogen interaction begins as soon as the seed germinates and develops into a seedling. Aphanomyces euteiches, an oomycete, stays dormant in soil and gets activated by sensing the host through chemical signals present in the root exudates. The composition of plant exudates may, thus, play an important role during the early phase of infection. To better understand the role of root exudates in plant resistance, we investigated the interaction between partially resistant lines (PI660736 and PI557500) and susceptible pea cultivars (CDC Meadow and AAC Chrome) against Aphanomyces euteiches during the pre-invasion phase. The root exudates of two sets of cultivars clearly distinguished from each other in inducing oospore germination. PI557500 root exudate not only had diminished induction but also inhibited the oospore germination. The contrast between the root exudates of resistance and susceptible cultivars was reflected in their metabolic profiles. Data from fractionation and oospore germination inhibitory experiments identified a group of saponins that accumulated differentially in susceptible and resistant cultivars. We detected 56 saponins and quantified 44 of them in pea root and 30 from root exudate; the majority of them, especially Soyasaponin I and dehydrosoyasaponin I with potent in vitro inhibitory activities, were present in significantly higher amounts in both roots and root exudates of PI660736 and PI557500 as compared to Meadow and Chrome. Our results provide evidence for saponins as deterrents against Aphanomyces euteiches, which might have contributed to the resistance against root rot in the studied pea cultivars.

Characterization of Neutral Lipids of the Oleaginous Alga Micractinum inermum.

An oleaginous microalga Micractinum inermum isolated from Mariana Lake, AB, Canada was cultured in a 1000 L photobioreactor with an f/2 medium to study its lipid content and neutral lipid profile. Algal biomass was collected at the stationary phase contained a significant amount of lipids (44.2%), as determined by Folch's method. The lipid was fractionated into neutral lipid, glycolipid and phospholipid fractions. The neutral lipid constitutes almost 77.3% of the total lipid species and is mainly composed of triacylglycerols (TAGs) determined by a proton NMR study. UHPLC-HRMS analysis allows us for the first time to identify 81 TAGs in the neutral lipid fraction of M. inermum. The fatty acid acyl side chains were identified based on fragment ions observed in MSMS analysis. TAGs with fatty acid acyl chains 18:1/18:1/18:1, 18:1/18:1/16:0, 18:2/18:1/16:0, and 18:2/18:2/18:0 were the major ones among the identified TAGs. Fatty acid analysis further supports the fact that oleic acid was the major fatty acid present in the neutral lipid fraction of M. inermum constituting 41.7%, followed by linoleic acid at 21.5%, and palmitic acid at 21.2%. The saturated and monounsaturated fatty acids were 67.8% or higher in the lipid fraction. Long-chain fatty acids were only present in a minor quantity. The results clearly demonstrate that M. inermum is an excellent source for TAGs.

Comprehensive Analysis of Biomass from Chlorella sorokiniana Cultivated with Industrial Flue Gas as the Carbon Source.

Chlorella sorokiniana, isolated from a pond adjacent to a cement plant, was cultured using flue gas collected directly from kiln emissions using 20 L and 25000 L photobioreactors. Lipids, proteins, and polysaccharides were analyzed to understand their overall composition for potential applications. The lipid content ranged from 17.97% to 21.54% of the dry biomass, with carotenoid concentrations between 8.4 and 9.2 mg/g. Lutein accounted for 55% of the total carotenoids. LC/MS analysis led to the identification of 71 intact triacylglycerols, 8 lysophosphatidylcholines, 10 phosphatidylcholines, 9 monogalactosyldiacylglycerols, 12 digalactosyldiacylglycerols, and 1 sulfoquinovosyl diacylglycerol. Palmitic acid, oleic acid, linoleic acid, and α-linolenic acid were the main fatty acids. Polyunsaturated fatty acid covers ≥ 56% of total fatty acids. Protein isolates and polysaccharides were also extracted. Protein purity was determined to be ≥75% by amino acid analysis, with all essential amino acids present. Monomer analysis of polysaccharides suggested that they are composed of mainly D-(+)-mannose, D-(+)-galactose, and D-(+)-glucose. The results demonstrate that there is no adverse effect on the metabolite profile of C. sorokiniana biomass cultured using flue gas as the primary carbon source, revealing the possibility of utilizing such algal biomass in industrial applications such as animal feed, sources of cosmeceuticals, and as biofuel.

Spin-Polarized Radicals with Extremely Long Spin-Lattice Relaxation Time at Room Temperature in a Metal-Organic Framework.

The generation of spin polarization is key in quantum information science and dynamic nuclear polarization. Polarized electron spins with long spin-lattice relaxation times (T1) at room temperature are important for these applications but have been difficult to achieve. We report the realization of spin-polarized radicals with extremely long T1 at room temperature in a metal-organic framework (MOF) in which azaacene chromophores are densely integrated. Persistent radicals are generated in the MOF by charge separation after photoexcitation. Spin polarization of a triplet generated by photoexcitation is successfully transferred to the persistent radicals. Pulse electron spin resonance measurements reveal that the T1 of the polarized radical in the MOF is as long as 214 µs with a relatively long spin-spin relaxation time T2 of the radicals of up to 0.98 µs at room temperature. The achievement of extremely long spin polarization in MOFs with nanopores accessible to guest molecules will be an important cornerstone for future highly sensitive quantum sensing and efficient dynamic nuclear polarization.

Production of quorum sensing-related metabolites and phytoalexins during Pseudomonas aeruginosa-Brassica napus interaction.

Pseudomonas aeruginosa is an opportunistic bacterial pathogen that has been shown to interact with many organisms throughout the domains of life, including plants. How this broad-host-range bacterium interacts with each of its diverse hosts, especially the metabolites that mediate these interactions, is not completely known. In this work, we used a liquid culture root infection system to collect plant and bacterial metabolites on days 1, 3 and 5 post-P. aeruginosa (strain PA14) infection of the oilseed plant, canola (Brassica napus). Using MS-based metabolomics approaches, we identified the overproduction of quorum sensing (QS)-related (both signalling molecules and regulated products) metabolites by P. aeruginosa while interacting with canola plants. However, the P. aeruginosa infection induced the production of several phytoalexins, which is a part of the hallmark plant defence response to microbes. The QS system of PA14 appears to only mediate part of the canola-P. aeruginosa metabolomic interactions, as the use of isogenic mutant strains of each of the three QS signalling branches did not significantly affect the induction of the phytoalexin brassilexin, while induction of spirobrassinin was significantly decreased. Interestingly, a treatment of purified QS molecules in the absence of bacteria was not able to induce any phytoalexin production, suggesting that active bacterial colonization is required for eliciting phytoalexin production. Furthermore, we identified that brassilexin, the only commercially available phytoalexin that was detected in this study, demonstrated a MIC of 400 µg ml-1 against P. aeruginosa PA14. The production of phytoalexins can be an effective component of canola innate immunity to keep potential infections by the opportunistic pathogen P. aeruginosa at bay.

Triacylglycerols and Other Lipids Profiling of Hemp By-Products.

Hemp seed by-products, namely hemp cake (hemp meal) and hemp hulls were studied for their lipid content and composition. Total lipid content of hemp cake and hemp hulls was 13.1% and 17.5%, respectively. Oil extraction yields using hexane, on the other hand, were much lower in hemp cake (7.4%) and hemp hulls (12.1%). Oil derived from both hemp seeds and by-products were primarily composed of neutral lipids (>97.1%), mainly triacylglycerols (TAGs), determined by SPE and confirmed by NMR study. Linoleic acid was the major fatty acid present in oils derived from hemp by-products, covering almost 55%, followed by α-linolenic acid, covering around 18% of the total fatty acids. For the first time, 47 intact TAGs were identified in the hemp oils using UPLC-HRMS. Among them, TAGs with fatty acid acyl chain 18:3/18:2/18:2 and 18:3/18:2/18:1 were the major ones, followed by TAGs with fatty acid acyl chain of 18:3/18:3/18:2, 18:2/18:2/16:0, 18:2/18:2/18:1, 18:3/18:2.18:0, 18:2/18:2/18:0, 18:2/18:1/18:1 and 18:3/18:2:16:0. Besides TAGs, low levels of terpenes, carotenoids and cannabidiolic acid were also detected in the oils. Moreover, the oils extracted from hemp by-products possessed a dose-dependent DPPH radical scavenging property and their potencies were in a similar range compared to other vegetable oils.

Analysis of Polar Lipids in Hemp (Cannabis sativa L.) By-Products by Ultra-High Performance Liquid Chromatography and High-Resolution Mass Spectrometry.

Polar lipids were extracted from residual biomass of hemp (Cannabis sativa L.) by-products with EtOH and partitioned into aqueous and chloroform fractions. The chloroform fractions were studied for their lipid composition using solid-phase extraction (SPE) followed by UHPLC/HRMS and NMR analyses. The 1H NMR and gravimetric yield of SPE indicated triacylglycerols covered ≥ 51.3% of the chloroform fraction of hemp seed hulls and hemp cake. UHPLC/HRMS analyses of remaining polar lipids led to the identification of nine diacylglycerols (DAGs), six lysophosphatidylcholines (LPCs), five lysophosphatidylethanolamines (LPEs), eight phosphatidylethanolamines (PEs), and thirteen phosphatidylcholines (PCs) for the first time from hemp seed hulls. The regiospecificity of fatty acyl substitutes in glycerol backbone of individual phospholipids were assigned by analyzing the diagnostic fragment ions and their intensities. The heat-map analysis suggested that DAG 18:2/18:2, 1-LPC 18:2, 1-LPE 18:2, PE 18:2/18:2, and PC 18:2/18:2 were the predominant molecules within their classes, supported by the fact that linoleic acid was the major fatty acid covering > 41.1% of the total fatty acids determined by GC-FID analysis. The 31P NMR analysis confirmed the identification of phospholipids and suggested PC covers ≥ 37.9% of the total phospholipid present in hemp by-products. HPLC purification led to the isolation of 1,2-dilinoleoylphosphatidylcholine and 1-palmitoyl-2-linoleoylphosphatidylcholine. These two major PCs further confirmed the UHPLC/HRMS finding.

Validation of Scolioscan Air-Portable Radiation-Free Three-Dimensional Ultrasound Imaging Assessment System for Scoliosis.

To diagnose scoliosis, the standing radiograph with Cobb's method is the gold standard for clinical practice. Recently, three-dimensional (3D) ultrasound imaging, which is radiation-free and inexpensive, has been demonstrated to be reliable for the assessment of scoliosis and validated by several groups. A portable 3D ultrasound system for scoliosis assessment is very much demanded, as it can further extend its potential applications for scoliosis screening, diagnosis, monitoring, treatment outcome measurement, and progress prediction. The aim of this study was to investigate the reliability of a newly developed portable 3D ultrasound imaging system, Scolioscan Air, for scoliosis assessment using coronal images it generated. The system was comprised of a handheld probe and tablet PC linking with a USB cable, and the probe further included a palm-sized ultrasound module together with a low-profile optical spatial sensor. A plastic phantom with three different angle structures built-in was used to evaluate the accuracy of measurement by positioning in 10 different orientations. Then, 19 volunteers with scoliosis (13F and 6M; Age: 13.6 ± 3.2 years) with different severity of scoliosis were assessed. Each subject underwent scanning by a commercially available 3D ultrasound imaging system, Scolioscan, and the portable 3D ultrasound imaging system, with the same posture on the same date. The spinal process angles (SPA) were measured in the coronal images formed by both systems and compared with each other. The angle phantom measurement showed the measured angles well agreed with the designed values, 59.7 ± 2.9 vs. 60 degrees, 40.8 ± 1.9 vs. 40 degrees, and 20.9 ± 2.1 vs. 20 degrees. For the subject tests, results demonstrated that there was a very good agreement between the angles obtained by the two systems, with a strong correlation (R2 = 0.78) for the 29 curves measured. The absolute difference between the two data sets was 2.9 ± 1.8 degrees. In addition, there was a small mean difference of 1.2 degrees, and the differences were symmetrically distributed around the mean difference according to the Bland-Altman test. Scolioscan Air was sufficiently comparable to Scolioscan in scoliosis assessment, overcoming the space limitation of Scolioscan and thus providing wider applications. Further studies involving a larger number of subjects are worthwhile to demonstrate its potential clinical values for the management of scoliosis.

Enhanced Electric Polarization and Polar Switching of Dipolar Aromatic Liquids Confined in Supramolecular Gel Networks.

Dipolar aromatic liquids confined in the interstitial domains of chiral organogels show significantly enhanced electric polarization, as compared with those of pure liquids alone or organogels formed with nonpolar liquids. Intriguingly, nitrobenzene gels showed a supramolecular polar switching phenomenon; i.e., hysteresis in the polarization (P)-electric field (E) curves was observed for the gel above the melting point of the solvent. This indicates that the nitrobenzene molecules confined in the chiral nanofibrous gel networks exert macroscopic polarization whose direction is inversed depending on the direction of the external electric field. The anomalously enhanced electric polarization and polar switching phenomenon of supramolecular gels in varied solvents are scrutinized by the positive-up-negative-down (PUND) measurements, and the interactions between the gel nanofibers and the polar solvent molecules play crucial roles for the emergence of the polar switching phenomenon. This work presents for the first time that dipolar liquid molecules filling the interstitial space of supramolecular gels exhibit a significant confinement effect. It provides a new perspective to design electric-field-responsive soft materials based on the functional liquid domains confined in their porous networks.

Ferroelectric Coordination Polymers Self-Assembled from Mesogenic Zinc(II) Porphyrin and Dipolar Bridging Ligands.

A new class of ferroelectric coordination-based polymers has been developed by the self-assembly of lipophilic zinc porphyrin (ZnP) and ditopic bridging ligands. The ligands contain dipolar benzothiadiazole or fluorobenzene units, which are axially coordinated to ZnP with the dipole moments oriented perpendicular to the coordination axes. The coordination-based polymers show ferroelectric characteristics in the liquid crystalline state, as revealed by distinctive hysteresis in the polarization-electric field (P-E) loops and inversion current peaks in current-voltage (I-V) loops. The observed ferroelectric properties are explainable by flip-flop rotation of the dipolar axle ligands induced by the applied electric field, as demonstrated by the positive-up-negative-down (PUND) measurements. The present system provides a new operating principle in supramolecular ferroelectrics.

Characterization of Shrimp Oil from Pandalus borealis by High Performance Liquid Chromatography and High Resolution Mass Spectrometry.

Northern shrimp (Pandalus borealis) oil, which is rich in omega-3 fatty acids, was recovered from the cooking water of shrimp processing facilities. The oil contains significant amounts of omega-3 fatty acids in triglyceride form, along with substantial long-chain monounsaturated fatty acids (MUFAs). It also features natural isomeric forms of astaxanthin, a nutritional carotenoid, which gives the oil a brilliant red color. As part of our efforts in developing value added products from waste streams of the seafood processing industry, we present in this paper a comprehensive characterization of the triacylglycerols (TAGs) and astaxanthin esters that predominate in the shrimp oil by using HPLC-HRMS and MS/MS, as well as 13C-NMR. This approach, in combination with FAME analysis, offers direct characterization of fatty acid molecules in their intact forms, including the distribution of regioisomers in TAGs. The information is important for the standardization and quality control, as well as for differentiation of composition features of shrimp oil, which could be sold as an ingredient in health supplements and functional foods.

Chirality in Singlet Fission: Controlling Singlet Fission in Aqueous Nanoparticles of Tetracenedicarboxylic Acid Ion Pairs.

The singlet fission characteristics of aqueous nanoparticles, self-assembled from ion pairs of tetracene dicarboxylic acid and various amines with or without chirality, are thoroughly investigated. The structure of the ammonium molecule, the counterion, is found to play a decisive role in determining the molecular orientation of the ion pairs and its regularity, spectroscopic properties, the strength of the intermolecular coupling between the tetracene chromophores, and the consequent singlet fission process. Using chiral amines has led to the formation of crystalline nanosheets and efficient singlet fission with a triplet quantum yield as high as 133% ±20% and a rate constant of 6.99 × 109 s-1. The chiral ion pairs also provide a separation channel to free triplets with yields as high as 33% ±10%. In contrast, nanoparticles with achiral counterions do not show singlet fission, which gave low or high fluorescence quantum yields depending on the size of the counterions. The racemic ion pair produces a correlated triplet pair intermediate by singlet fission, but no decorrelation into two free triplets is observed, as triplet-triplet annihilation dominates. The introduction of chirality enables higher control over orientation and singlet fission in self-assembled chromophores. It provides new design guidelines for singlet fission materials.

Photoliquefaction and phase transition of m-bisazobenzenes give molecular solar thermal fuels with a high energy density.

A series of m-bisazobenzene chromophores modified with various alkoxy substituents (1; methoxy, 2; ethoxy, 3; butoxy, 4; neopentyloxy) were developed for solvent-free molecular solar thermal fuels (STFs). Compounds (E,E)-1-3 in the crystalline thin film state exhibited photoliquefaction, the first example of photo-liquefiable m-bisazobenzenes. Meanwhile, (E,E)-4 did not show photoliquefaction due to the pronounced rigidity of the interdigitated molecular packing indicated by X-ray crystallography. The m-bisazobenzenes 1-4 exhibited twice the Z-to-E isomerization enthalpy compared to monoazobenzene derivatives, and the latent heat associated with the liquid-solid phase change further enhanced their heat storage capacity. To observe both exothermic Z-to-E isomerization and crystallization in a single heat-up process, the temperature increase of differential scanning calorimetry (DSC) must occur at a rate that does not deviate from thermodynamic equilibrium. Bisazobenzene 1 showed an unprecedented gravimetric heat storage capacity of 392 J g-1 that exceeds previous records for well-defined molecular STFs.

Plant Growth-Promoting Rhizobacteria (PGPR) with Microbial Growth Broth Improve Biomass and Secondary Metabolite Accumulation of Cannabis sativa L.

Plant growth-promoting rhizobacteria (PGPR) are a sustainable crop production input; some show positive effects under laboratory conditions but poorly colonize host field-grown plants. Inoculating with PGPR in microbial growth medium (e.g., King's B) could overcome this. We evaluated cannabis plant (cv. CBD Kush) growth promotion by inoculating three PGPR (Bacillus sp., Mucilaginibacter sp., and Pseudomonas sp.) in King's B at vegetative and flower stages. At the vegetative stage, Mucilaginibacter sp. inoculation increased flower dry weight (24%), total CBD (11.1%), and THC (11.6%); Pseudomonas sp. increased stem (28%) dry matter, total CBD (7.2%), and THC (5.9%); and Bacillus sp. increased total THC by 4.8%. Inoculation with Mucilaginibacter sp. and Pseudomonas sp. at the flowering stage led to 23 and 18% increases in total terpene accumulation, respectively. Overall, vegetative inoculation with PGPR enhanced cannabis yield attributes and chemical profiles. Further research into PGPR inoculation onto cannabis and the subsequent level of colonization could provide key insights regarding PGPR-host interactions.

Strategic identification of in vitro metabolites of 13-desmethyl spirolide C using liquid chromatography/high-resolution mass spectrometry.

A strategy to identify metabolites of a marine biotoxin, 13-desmethyl spirolide C, has been developed using liquid chromatography coupled to high-resolution mass spectrometry (LC/HRMS). Metabolites were generated in vitro through incubation with human liver microsomes. A list of metabolites was established by selecting precursor ions of a common fragment ion characteristic of the spirolide toxin which was known to contain a cyclic imine ring. Accurate mass measurements were subsequently used to confirm the molecular formula of each biotransformation product. Using this approach, a total of nine phase I metabolites was successfully identified with deviations of mass accuracy less than 2 ppm. The biotransformations observed included hydroxylation, dihydroxylation, oxidation of a quaternary methyl group to hydroxymethyl or carboxylic acid groups, dehydrogenation and hydroxylation, as well as demethylation and dihydroxylation reactions. In a second step, tandem mass spectrometry (MS/MS) was performed to elucidate structures of the metabolites. Using the unique fragment ions in the spectra, the structures of the three major metabolites, 13,19-didesmethyl-19-carboxy spirolide C, 13,19-didesmethyl-19-hydroxymethyl spirolide C and 13-desmethyl-17-hydroxy spirolide C, were assigned. Levels of 13-desmethyl spirolide C and its metabolites were monitored at selected time points over a 32-h incubation period with human liver microsomes. It was determined that 13,19-didesmethyl-19-carboxy spirolide C became the predominant metabolite after 2 h of incubation. The stability plot of 13-desmethyl spirolide C showed first-order kinetics for its metabolism and the intrinsic clearance was calculated to be 41 µL/min/mg, suggesting first-pass metabolism may contribute to limiting oral toxicity of 13-desmethyl spirolide C.

Self-assembly of a catechol-based macrocycle at the liquid-solid interface: experiments and molecular dynamics simulations.

This combined experimental (STM, XPS) and molecular dynamics simulation study highlights the complex and subtle interplay of solvent effects and surface interactions on the 2-D self-assembly pattern of a Schiff-base macrocycle containing catechol moieties at the liquid-solid interface. STM imaging reveals a hexagonal ordering of the macrocycles at the n-tetradecane/Au(111) interface, compatible with a desorption of the lateral chains of the macrocycle. Interestingly, all the triangular-shaped macrocycles are oriented in the same direction, avoiding a close-packed structure. XPS experiments indicate the presence of a strong macrocycle-surface interaction. Also, MD simulations reveal substantial solvent effects. In particular, we find that co-adsorption of solvent molecules with the macrocycles induces desorption of lateral chains, and the solvent molecules act as spacers stabilizing the open self-assembly pattern.

9,10-Dihydro-5-hydroxy-2,3,6-trimethoxyphenanthrene-1,4-dione: a new dihydrophenanthrene from commercial cannabis and its effect on zebrafish larval behaviour.

A new dihydrophenanthrene derivative namely 9,10-dihydro-5-hydroxy-2, 3,6-trimethoxyphenanthrene-1,4-dione (1) was isolated from commercial cannabis product together with 4,5-dihydroxy-2,3,6-trimethoxy-9,10-dihydrophenanthrene (2), 4-hydroxy-2,3,6,7-tetramethoxy-9,10-dihydrophenanthrene (3), combretastatin B-2 (4) and isocannbispiradienone (5). Structure elucidation of the isolated compounds were done based on the interpretation of the mass spectrometry (MS) and nuclear magnetic resonance (NMR) data. New dihydrophenanthrene derivative (1) was tested for its effect on zebrafish larval behaviour. Preliminary results suggested that the new dihydrophenanthrene derivative (1) exhibits similar effect on zebrafish larval behaviour as cannabidiol (CBD), a biologically active component of Cannabis.

Evaluation of the Uptake, Metabolism, and Secretion of Toxicants by Zebrafish Larvae.

Zebrafish larvae have classically been used as a high-throughput model with which to test both the bioactivity and toxicity of known and novel compounds, making them a promising whole organism New Approach Method in the context of the international momentum to eliminate animal testing. Larvae are generally exposed to the chemicals being tested in a static environment and the concentration-response patterns are calculated based on the initial bath concentrations of the compounds. This approach rarely takes into account the absorption, distribution, metabolism, and excretion of the compounds being tested, which can have a significant effect on the toxicokinetic profiles of the compounds and thus impact the predictive ability of the model. In this study, we have evaluated the toxicokinetic profile of 5 known toxicants, 3 phenolic compounds, along with thiabendazole and 3,4-dicholoronalanine, at 6, 8, 24, 72, and 120 h postfertilization in order to match the exposure timelines of a standard in vitro fish embryo toxicity test. It was revealed that in addition to bioaccumulation effects, the compounds were all actively metabolized and excreted by the larvae. Importantly, comparisons between the toxicants revealed that the patterns of uptake and metabolism were varied and could often partially explain the differences in their concentration-response patterns. The findings of this study are significant as they highlight the requirement for an assessment of the stability and toxicokinetic profile of chemicals tested using standard zebrafish larval toxicity assays in order to better understand and compare their toxicity profiles.

Molecular characterization of zebrafish embryogenesis via DNA microarrays and multiplatform time course metabolomics studies.

One of the greatest strengths of "-omics" technologies is their ability to capture a molecular snapshot of multiple cellular processes simultaneously. Transcriptomics, proteomics, and metabolomics have, individually, been used in wide-ranging studies involving cell lines, tissues, model organisms, and human subjects. Nonetheless, despite the fact that their power lies in the global acquisition of parallel data streams, these methods continue to be employed separately. We highlight work done to merge transcriptomics and metabolomics technologies to study zebrafish (Danio rerio) embryogenesis. We combine information from three bioanalytical platforms, that is, DNA microarrays, (1)H nuclear magnetic resonance ((1)H NMR), and mass spectrometry (MS)-based metabolomics, to identify and provide insights into the organism's developmental regulators. We apply a customized approach to the analysis of such time-ordered measurements to provide temporal profiles that depict the modulation of metabolites and gene transcription. Initially, the three data sets were analyzed individually but later they were fused to highlight the advantages gained through such an integrated approach. Unique challenges posed by fusion of such data are discussed given differences in the measurement error structures, the wide dynamic range for the molecular species, and the analytical platforms used to measure them (i.e., fluorescence ratios, NMR, and MS intensities). Our data analysis reveals that changes in transcript levels at specific developmental stages correlate with previously published data with over 90% accuracy. In addition, transcript profiles exhibited trends that were similar to the accumulation of metabolites over time. Profiles for metabolites such as choline-like compounds (Trimethylamine-N-oxide, phosphocholine, betaine), creatinine/creatine, and other metabolites involved in energy metabolism exhibited a steady increase from 15 hours post fertilization (hpf) to 48 hpf. Other metabolite and transcript profiles were transiently rising and then falling back to baseline. The "house keeping" metabolites such as branched chain amino acids exhibited a steady presence throughout embryogenesis. Although the transcript profiling corresponds to only 16 384 genes, a subset of the total number of genes in the zebrafish genome, we identified examples where gene transcript and metabolite profiles correlate with one another, reflective of a relationship between gene and metabolite regulation over the course of embryogenesis.

Prussian blue nanocontainers: selectively permeable hollow metal-organic capsules from block ionomer emulsion-induced assembly.

Hollow polymer-based particles are useful for the encapsulation, protection, and release of active compounds. Adding a metal-organic coordination framework shell to nanocontainers is an attractive goal because it should help control their stability and permeability while yielding new properties and functions. We have discovered that polymer capsules with a Prussian blue analogue inner shell can be synthesized by emulsion-induced assembly of a metal-containing amphiphilic block ionomer. The capsules are selectively permeable and were used as nanocontainers to encapsulate and release a model compound. Further, these nanomaterials are tunable in size and organize into 2-D close-packed arrays in the solid state. Potential applications for these materials include the encapsulation and nanopatterning of pharmaceutical, biological, and catalytic compounds.