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Developed as part of a larger effort by the National Weather Service (NWS) Radar Operations Center to modernize their suite of single-radar severe weather algorithms for the WSR-88D radar network, the Tornado Probability algorithm (TORP) and the New Mesocyclone Detection Algorithm (NMDA) were evaluated by operational forecasters during the 2021 National Oceanic and Atmospheric Administration (NOAA) Hazardous Weather Testbed (HWT) Experimental Warning Program Radar Convective Applications experiment. Both TORP and NMDA leverage new products and advances in radar technology to create rotation-based objects that interrogate single-radar data, providing important summary and trend information that aids forecasters in issuing time-critical and potentially life-saving weather products. Utilizing virtual resources like Google Workspace and cloud instances on Amazon Web Services, 18 forecasters from the NOAA NWS and the United States Air Force participated remotely over three weeks during the spring of 2021, providing valuable feedback on the efficacy of the algorithms and their display in an operational warning environment, serving as a critical step in the research-to-operations process for the development of TORP and NMDA. This article will discuss the details of the virtual HWT experiment and the results of each algorithm’s evaluation during the testbed.

The local, linear, least squares derivative (LLSD) approach to radar analysis is a method of quantifying gradients in radar data by fitting a least squares plane to a neighborhood of range bins and finding its slope. When applied to radial velocity fields, for example, LLSD yields part of the azimuthal (rotational) and radial (divergent) components of horizontal shear, which, under certain geometric assumptions, estimate one-half of the two-dimensional vertical vorticity and horizontal divergence equations, respectively. Recent advances in computational capacity as well as increased usage of LLSD products by the meteorological community have motivated an overhaul of the LLSD methodology’s application to radar data. This paper documents the mathematical foundation of the updated LLSD approach, including a complete derivation of its equation set, discussion of its limitations, and considerations for other types of implementation. In addition, updated azimuthal shear calculations are validated against theoretical vorticity using simulated circulations. Applications to nontraditional radar data and new applications to nonvelocity radar data including reflectivity at horizontal polarization, spectrum width, and polarimetric moments are also explored. These LLSD gradient calculations may be leveraged to identify and interrogate a wide variety of severe weather phenomena, either directly by operational forecasters or indirectly as part of future automated algorithms.

Synthetic studies toward maoecrystal V are reported. An oxidative dearomatization/Diels-Alder cascade to assemble the natural product carbocyclic core in one step is proposed. A facile electrocyclization is shown to suppress the intramolecular allene Diels-Alder pathway. This obstacle is alleviated via a stepwise approach with an allene equivalent to access the key cyclopentadiene-fused [2.2.2]-bicyclic core. Upon treatment with Lewis acid, the proposed intramolecular hetero-Diels-Alder reaction is cleanly and unexpectedly diverted either via C-C bond-forming fragmentation to the spiro-indene product (when R = OMe) or via elimination (when R = H).

There are numerous challenges with the forecasting and detection of flash floods, one of the deadliest weather phenomena in the United States. Statistical metrics of flash flood warnings over recent years depict a generally stagnant warning performance, while regional flash flood guidance utilized in warning operations was shown to have low skill scores. The Hydrometeorological Testbed—Hydrology (HMT-Hydro) experiment was created to allow operational forecasters to assess emerging products and techniques designed to improve the prediction and warning of flash flooding. Scientific goals of the HMT-Hydro experiment included the evaluation of gridded products from the Multi-Radar Multi-Sensor (MRMS) and Flooded Locations and Simulated Hydrographs (FLASH) product suites, including the experimental Coupled Routing and Excess Storage (CREST) model, the application of user-defined probabilistic forecasts in experimental flash flood watches and warnings, and the utility of the Hazard Services software interface with flash flood recommenders in real-time experimental warning operations. The HMT-Hydro experiment ran in collaboration with the Flash Flood and Intense Rainfall (FFaIR) experiment at the Weather Prediction Center to simulate the real-time workflow between a national center and a local forecast office, as well as to facilitate discussions on the challenges of short-term flash flood forecasting. Results from the HMT-Hydro experiment highlighted the utility of MRMS and FLASH products in identifying the spatial coverage and magnitude of flash flooding, while evaluating the perception and reliability of probabilistic forecasts in flash flood watches and warnings. NSSL scientists and NWS forecasters evaluate new tools and techniques through real-time test bed operations for the improvement of flash flood detection and warning operations.

Monitoring mechanisms are an essential component of timing security. Existing mechanisms allow for a comprehensive view of the distribution of time throughout a network, but they do not scale to large networks. We propose a new method called aggregated reverse time transfer (ARTT), which builds upon the reverse time transfer mechanism and the IEEE 1588 monitoring TLV to limit message complexity and redundant information. We demonstrate that these two mechanisms can be used in concert to report the timing error of a network more efficiently without a significant loss in accuracy.

Synthetic approaches toward the complex natural product diterpenoid maoecrystal V are reviewed, including successful total syntheses, published synthetic efforts, and efforts compiled from dissertations. The review focuses on general synthetic strategies and chronicles efforts toward the molecule since its isolation in 2004, summarizing key contributions of these efforts to the broader synthetic community.

The diversity of elements among U.S. Food and Drug Administration (FDA) approved pharmaceuticals is analyzed and reported, with a focus on atoms other than carbon, hydrogen, oxygen, and nitrogen. Our analysis reveals that sulfur, chlorine, fluorine, and phosphorous represent about 90% of elemental substitutions, with sulfur being the fifth most used element followed closely by chlorine, then fluorine and finally phosphorous in the eighth place. The remaining 10% of substitutions are represented by 16 other elements of which bromine, iodine, and iron occur most frequently. The most detailed parts of our analysis are focused on chlorinated drugs as a function of approval date, disease condition, chlorine attachment, and structure. To better aid our chlorine drug analyses, a new poster showcasing the structures of chlorinated pharmaceuticals was created specifically for this study. Phosphorus, bromine, and iodine containing drugs are analyzed closely as well, followed by a discussion about other elements.

The tornado that affected Moore, Oklahoma, and the surrounding area on 20 May 2013 was an extreme event. It traveled 23 km and damage was up to 1.7 km wide. The tornado killed 24 people, injured over 200 others, and damaged many structures. A team of surveyors from the Norman, Oklahoma, National Weather Center and two private companies performed a detailed survey (all objects/structures) of the tornado to provide better documentation than is normally done, in part to aid future studies of the event. The team began surveying tornado damage on the morning of 21 May and continued the survey process for the next several weeks. Extensive ground surveys were performed. The surveys were aided by use of high-resolution aerial and satellite imagery. The survey process utilized the enhanced Fujita (EF) scale and was facilitated by use of a National Weather Service (NWS) software package: the Damage Assessment Toolkit (DAT). The survey team defined a “well built” house that qualified for an EF5 rating. Survey results document 4253 objects damaged by the tornado, 4222 of them EF-scale damage indicators (DIs). Of the total DIs, about 50% were associated with EF0 ratings. Excluding EF0 damage, 38% were associated with EF1, 24% with EF2, 21% with EF3, 17% with EF4, and only 0.4% associated with EF5. For the strongest level of damage (EF5), only nine homes were found. Survey results are similar to other documented tornadoes, but the amount of EF1 damage is greater than in other cases. Also discussed is the use of non-DI objects that are damaged and ways in which to improve future surveys.

The evolution of the synthetic strategy resulting in a total synthesis of vinigrol is presented. Oxidative dearomatization/intramolecular Diels-Alder cycloaddition has served as the successful cornerstone for all of the approaches. Extensive radical cyclization efforts to form the tetracyclic core resulted in interesting and surprising reaction outcomes, none of which could be advanced to vinigrol. These cyclization obstacles were successfully overcome by using Heck instead of radical cyclizations. The total synthesis features a trifluoroethyl ether protecting group being used for the first time in organic synthesis. The logic of its selection and the group's importance beyond protecting the C8a hydroxyl group is presented along with a discussion of strategies for its removal. Because of the compact tetracyclic cage the route is built around many unusual reaction observations and solutions have emerged. For example, a first of its kind Grob fragmentation reaction featuring a trifluoroethyl leaving group has been uncovered, interesting interrupted selenium dioxide allylic oxidations have been observed as well as intriguing catalyst and counterion dependent directed hydrogenations.

The Great Plains region of the United States is susceptible to drought of all kinds including meteorological/climatological, agricultural, hydrological, and socioeconomic. Drought conditions in the region span varying spatial and temporal scales and the causes include: 1) certain synoptic conditions that favor drought such as mid-tropospheric ridging over the drought-affected area and a weak low-level jet; 2) sea surface temperature anomalies and associated teleconnections; 3) land-atmosphere coupling; and 4) anthropogenic effects. While drought can span as few as a couple of months, the most severe droughts can occur at the decadal scale such as the 1930s Dust Bowl, the worst drought in recent history from a societal standpoint. Such droughts in the Great Plains have widespread impacts on agriculture, water resources, human health, and the economy.

Seedlings of sweet orange (Citrus sinensis) were fertilized for 14 weeks with boron (B)-free or B-sufficient (2.5 or 10 microM H(3)BO(3)) nutrient solution every other day. Boron deficiency resulted in an overall inhibition of plant growth, with a reduction in root, stem and leaf dry weight (DW). Boron-starved leaves showed decreased CO(2) assimilation and stomatal conductance, but increased intercellular CO(2) concentrations. Activities of ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco), NADP-glyceraldehyde-3-phosphate dehydrogenase (NADP-GAPDH) and stromal fructose-1,6-bisphosphatase (FBPase) were lower in B-deficient leaves than in controls. Contents of glucose, fructose and starch were increased in B-deficient leaves while sucrose was decreased. Boron-deficient leaves displayed higher or similar superoxide dismutase (SOD), ascorbate peroxidase (APX), monodehydroascorbate reductase (MDAR) and glutathione reductase (GR) activities, while dehydroascorbate reductase (DHAR) and catalase (CAT) activities were lower. Expressed on a leaf area or protein basis, B-deficient leaves showed a higher ascorbate (AsA) concentration, but a similar AsA concentration on a DW basis. For reduced glutathione (GSH), we found a similar GSH concentration on a leaf area or protein basis and an even lower content on a DW basis. Superoxide anion (O(2)(-)) generation, malondialdehyde (MDA) concentration and electrolyte leakage were higher in B-deficient than in control leaves. In conclusion, CO(2) assimilation may be feedback-regulated by the excessive accumulation of starch and hexoses in B-deficient leaves via direct interference with chloroplast function and/or indirect repression of photosynthetic enzymes. Although B-deficient leaves remain high in activity of antioxidant enzymes, their antioxidant system as a whole does not provide sufficient protection from oxidative damage.

‘Concord’ grapevines (Vitis labruscana Bailey) are susceptible to lime-induced chlorosis, which decreases growth and productivity. In two separate experiments, we grew own-rooted vines in a peat–perlite medium adjusted to different pHs with CaCO3 to characterize how lime-induced Fe deficiency affects root and leaf ferric chelate reductase (FCR) and key enzymes and metabolites involved with glycolysis and the tricarboxylic acid (TCA) cycle in leaves. In addition, we measured the pH of the xylem sap as well as Fe, citrate, and malate concentrations. For both experiments, foliar levels of total Fe, active Fe (extracted in 0.1N HCl), and chlorophyll decreased as lime rate increased. An increase in root-medium pH from 5.8 to 7.5 resulted in a 10-fold increase in root FCR activity, whereas leaf FCR activity decreased 10-fold. An increase in root-medium pH did not raise xylem sap pH but decreased Fe and citrate to some extent. Xylem malate was highest at pH 6.6 and decreased both above and below this pH. Foliar data were evaluated in relation to active Fe content, because it is a better indicator of Fe nutritional status. Lower active Fe decreased midday CO2 assimilation and PSII quantum efficiency as well as night respiration. As active Fe decreased, aconitase activity decreased linearly, whereas the activity of glucose-6-phosphate dehydrogenase, NAD(P)-isocitrate dehydrogenase, NAD(P)-malic enzyme, malate dehydrogenase, phosphoenolpyruvate (PEP) carboxylase, PEP phosphatase, and pyruvate kinase increased curvilinearly. Glucose-6-phosphate, fructose-6-phosphate, and 3-phosphoglycerate content decreased curvilinearly as active Fe decreased. Malate content increased as active Fe increased to 1.0 mg·m−2 and then decreased above this level. Citrate increased linearly as active Fe decreased and was an order of magnitude lower than malate content. Our results suggest that leaf FCR activity may limit Fe assimilation to a greater extent than root FCR activity. The decreased leaf aconitase activity under Fe deficiency is the most likely cause of the increase in citrate levels. Greater activity of the other glycolytic and TCA enzymes under Fe deficiency may help to funnel carbon into the mitochondria and enhance NAD(P) reduction. Citrate levels (and the citrate:malate ratios) in the xylem exudate and leaf were much lower when compared with other species and may be linked to Fe inefficiency of ‘Concord’.

Concord grapevines (Vitis labruscana Bailey) can readily develop iron deficiency-induced leaf chlorosis when grown on calcareous or high pH soils. Iron (Fe) chelates are often applied to the soil to remedy chlorosis but can vary in their stability and effectiveness at high pH. We transplanted own-rooted 1-year-old Concord grapevines into a peat-based medium adjusted to pH 7.5 and fertigated them with 0, 0.5, 1.0, 2.0, or 4m gL -1 Fe from Fe-EDDHA (ferric ethylenediamine di (o-hydroxyphenylacetic) acid) to determine the effectiveness of this Fe chelate for alleviating Fe deficiency-induced chlorosis at high pH. Vines were sampled midseason for iron, chlorophyll, CO2 assimilation, and photosystem II quantum efficiency (PSII) and at the end of the season for leaf area, dry weight, and cane length. We found that leaf total Fe concentration was similar across all treatments, but active Fe (extracted with 0.1 N HCl) concentration increased as the rate of Fe-EDDHA increased. Chlorophyll concentration increased curvilinearly as applied Fe increased and was highly correlated with active Fe concentration. CO2 assimilation, stomatal conductance, and PSII were very low without any supplemental Fe and increased rapidly in response to Fe application. Total leaf area, foliar dry weight, and cane length all increased as Fe application increased to 1 mgL -1 Fe, but above this rate, a further increase in Fe did not significantly increase growth. Our results demonstrate that Fe-EDDHA is very effective in alleviating Fe deficiency-induced leaf chlorosis in Concord grapevines grown at high pH, which provides a foundation for continuing research related to the optimum rate and timing of application of Fe-EDDHA in Concord vineyards on calcareous soils. Compared with total Fe, leaf ''active Fe'' better indicates the actual Fe status of Concord vines. Concord grapevines (Vitis labruscana Bailey) are native to the northeastern United States (Schofield, 1988) and are tolerant of the acidic soils that characterize the region. As soil pH increases and iron (Fe) becomes less available, own-rooted Concord grape- vines can readily develop Fe deficiency- induced leaf chlorosis. In Concord vine- yards where calcareous or high pH soils predominate such as in Washington State, leaf chlorosis can be a limiting factor in production (Davenport and Stevens, 2006). Iron is a key nutrient in a number of metabolic pathways. The major symptom of Fe deficiency is chlorosis as a result of the requirement for Fe in protochlorophyllide synthesis (Tottey et al., 2003). Fe is essential in reactions that regulate CO2 assimilation and antioxidant protection, and we have shown that Fe-deficient source leaves have lower levels of nonstructural carbohydrates

Two experiments were conducted to evaluate effects of water-soluble fertilizer concentration (WSF) and substrate-pH on growth, foliar nutrient content, and chlorosis of seed geranium (Pelargonium × hortorum) “Ringo Scarlet.” Geraniums were grown for 21 days in a 70% peat-30% perlite substrate. Experiment 1 included four pre-plant lime rates (pH 3.8, 4.3, 4.8, and 5.5), and plants were irrigated using 1X, 2X, 3X, and 4X rates of a WSF containing 75N-11P-84K-72Ca-17 Mg-23S-0.375Fe-0.185 Mn-0.019Zn-0.028Cu-0.058B-0.006Mo. Iron (Fe), manganese (Mn), zinc (Zn), and copper (Cu) were supplied as EDTA-chelated micronutrients. Experiment 2 included six lime rates (initial pH 3.2, 4.3, 5.2, 6.3, 7.0, and 7.5) at 2X and 4X WSF concentrations. Two forms of chlorosis were observed, consistent with micronutrient toxicity at moderately-low pH (4.3–5.2) and micronutrient deficiency at pH above 6.3. At very low substrate-pH, below 4.0, cation content decreased in leaf tissue, anion content increased, and plants a...

The objective was to quantify the effect of substrate pH and micronutrient concentration on tissue nutrient levels in Petunia ×hybrida Hort. Vilm.-Andr. and Impatiens wallerana Hook. F. Plants were grown in 10-cm-diameter pots for 4 weeks in a 70% peat: 30% perlite medium amended with five lime rates to achieve substrate pH values ranging from pH 4.4 to 7.0. Plants were irrigated with (in mg·L-1) 210N-31P-235K-200Ca-49Mg. Micronutrients were applied as an EDTA (ethylenedinitrilotetraacetic acid) chelated micronutrient blend (C111), at 1×, 2×, and 4× concentrations of 0.50Fe-0.25Mn-0.025Zn-0.04Cu-0.075B-0.01Mo. Patterns of tissue concentrations across substrate pH differed from nutrient solubility in the medium, particularly with regard to Mn. Foliar N content decreased slightly as substrate pH increased, whereas foliar Ca, Mg, and S increased. Although foliar P and K varied with pH, there was no consistent trend between species. Foliar total Fe, ferrous Fe, and Cu decreased as substrate pH increased, whereas foliar Zn increased. Foliar Mn content decreased for both species as pH rose to 6.0, and then increased from pH 6.0 to 7.0. In contrast, Mn level in the substrate, measured in a saturated medium extract using deionized water as the extractant, decreased as pH increased from pH 4.4 to 7.0. Chlorophyll content decreased when the ratio of tissue Fe to Mn was -1. SPAD chlorophyll index also declined in petunia with foliar Mn >42 μg·g-1. Increasing C111 increased foliar Cu, total Fe and ferrous Fe in both species, and B for impatiens, and partly compensated for reduced nutrient solubility at high pH.

The objective was to quantify the effect of substrate pH and micronutrient concentration on growth and pigment content for two floricultural crop species, Petunia ×hybrida `Priscilla' and Impatiens wallerana `Rosebud Purple Magic'. A 70% peat: 30% perlite medium was amended with dolomitic hydrated lime to achieve five substrate pH's ranging from pH 4.4 to 7.0. Plants were grown in 10-cm-diameter pots in a greenhouse for 4 weeks, and irrigated with a fertilizer containing (in mg·L-1) 210N-31P-235K-200Ca-49Mg. Micronutrients were applied using an EDTA (ethylenedinitrilotetraacetic acid) chelated micronutrient blend (C111), at 1×, 2×, and 4× concentrations (in mg·L-1) of 0.50Fe-0.25Mn-0.025Zn-0.04Cu-0.075B-0.01Mo. Petunia shoot dry mass and stem caliper decreased as substrate pH increased, whereas leaf length and width remained unchanged. The highest level of C111 resulted in higher dry mass and smaller leaf area compared with other C111 levels. Overall, substrate pH and C111 had little effect on plant size or mass for impatiens. For both species, increasing substrate pH above 5.3 resulted in a decline in chlorophyll, carotenoids, and the SPAD chlorophyll index (measured with a Minolta-502 SPAD meter) compared with the lowest three pH levels. Chlorosis was observed at pH 7 after 2 weeks of growth. Increasing C111 concentration had no effect on pigment content below pH 5.3, but increased pigment content at higher pH levels. The SPAD index was highly correlated with chlorophyll content. This research emphasizes that an acceptable range in substrate pH can vary depending on fertilizer practices, with higher micronutrient concentration compensating for lower solubility at high substrate pH.

ADDITIONAL INDEX WORDS. active Fe, ADP-glucose pyrophosphorylase (AGPase), fructose-1,6-bisphosphatase (FBPase), NADP-glyceraldehyde-3-phosphate dehydrogenase (GAPDH), phosphoribulokinase (PRK), ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco), starch, sucrose phosphate synthase (SPS) ABSTRACT. Own-rooted 1-year-old ʻConcordʼ grapevines (Vitis labruscana Bailey) were fertigated twice weekly for 11 weeks with 1, 10, 20, 50, or 100 µM iron (Fe) from ferric ethylenediamine di (o-hydroxyphenylacetic) acid (Fe-EDDHA) in a complete nutrient solution. As Fe supply increased, leaf total Fe content did not show a signifi cant change, whereas active Fe (extracted by 2,2´-dipyridyl) content increased curvilinearly. Chlorophyll (Chl) content increased as Fe sup- ply increased, with a greater response at the lower Fe rates. Chl a : b ratio remained relatively constant over the range of Fe supply, except for a slight increase at the lowest Fe treatment. Both CO2 assimilation and stomatal conductance increased curvilinearly with increasing leaf active Fe, whereas intercellular CO2 concentrations decreased linearly. Activities of key enzymes in the Calvin cycle, ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco), NADP-glyc- eraldehyde-3-phosphate dehydrogenase (GAPDH), phosphoribulokinase (PRK), stromal fructose-1,6-bisphosphatase (FBPase), and a key enzyme in sucrose synthesis, cytosolic FBPase, all increased linearly with increasing leaf active Fe. No signifi cant difference was found in the activities of ADP-glucose pyrophosphorylase (AGPase) and sucrose phosphate synthase (SPS) of leaves between the lowest and the highest Fe treatments, whereas slightly lower activities of AGPase and SPS were observed in the other three Fe treatments. Content of 3-phosphoglycerate (PGA) increased curvilinearly with increasing leaf active Fe, whereas glucose-6-phosphate (G6P), fructose-6-phosphate (F6P), and the ratio of G6P : F6P remained unchanged over the range of Fe supply. Concentrations of glucose, fructose, sucrose, starch, and total nonstructural carbohydrates (TNC) at both dusk and predawn increased with increasing leaf active Fe. Concentrations of starch and TNC at any given leaf active Fe content were higher at dusk than at predawn, but both glucose and fructose showed the opposite trend. No difference in sucrose concentration was found at dusk or predawn. The export of carbon from starch breakdown during the night, calculated as the difference between dusk and predawn measurements, increased as leaf active Fe content increased. The ratio of starch to sucrose at both dusk and predawn also increased with increasing leaf active Fe. In conclusion, Fe limitation reduces the activities of Rubisco and other photosynthetic enzymes, and hence CO2 assimilation capacity. Fe-defi cient grapevines have lower concentrations of nonstructural carbohydrates in source leaves and, therefore, are source limited.

The objective was to evaluate and compare foliar spray and soil drench application methods of iron (Fe) for correcting Fe deficiency in hybrid calibrachoa (Calibrachoa × hybrida) grown in a container medium at pH 6.9 to 7.4. Untreated plants showed severe chlorosis and necrosis, stunting, and lack of flowering. An organosilicone surfactant applied at 1.25 mL·L-1 (0.160 fl oz/gal) increased uptake of Fe from foliar applications of both ferrous sulfate (FeSO4) and ferric ethylenediamine tetraacetic acid (Fe-EDTA). Foliar sprays at 60 mg·L-1 (ppm) Fe were more effective when Fe was applied as Fe-EDTA than FeSO4. Increasing Fe concentration of foliar sprays up to 240 mg·L-1 Fe from Fe-EDTA or 368 mg·L-1 Fe (the highest concentrations tested) from ferric diethylenetriamine pentaacetic acid (Fe-DTPA) increased chlorophyll content compared with lower spray concentrations, but leaf necrosis at the highest concentrations may have been caused by phytotoxicity. Drenches with ferric ethylenediaminedi(o-hydroxyphenylacetic) acid (Fe-EDDHA) at 20 to 80 mg·L-1 Fe were highly effective at correcting Fe-deficiency symptoms, and had superior effects on plant growth compared with drenches of Fe-DTPA at 80 mg·L-1 Fe or foliar sprays. Efficacy of Fe-DTPA drenches increased as concentration increased from 20 to 80 mg·L-1 Fe. An Fe-EDDHA drench at 20 to 80 mg·L-1 Fe was a cost-effective option for correcting severe Fe deficiency at high medium pH.

The diversity of elements among U.S. Food and Drug Administration (FDA) approved pharmaceuticals is analyzed and reported, with a focus on atoms other than carbon, hydrogen, oxygen, and nitrogen. Our analysis reveals that sulfur, chlorine, fluorine, and phosphorous represent about 90% of elemental substitutions, with sulfur being the fifth most used element followed closely by chlorine, then fluorine and finally phosphorous in the eighth place. The remaining 10% of substitutions are represented by 16 other elements of which bromine, iodine, and iron occur most frequently. The most detailed parts of our analysis are focused on chlorinated drugs as a function of approval date, disease condition, chlorine attachment, and structure. To better aid our chlorine drug analyses, a new poster showcasing the structures of chlorinated pharmaceuticals was created specifically for this study. Phosphorus, bromine, and iodine containing drugs are analyzed closely as well, followed by a discussion about other elements.

Self-rooted, 10-month-old, uniform tea [Camellia sinensis (L.) O. Kuntze cv. Huangguanyin] plants were supplied for 17 weeks with 0, 40, 80, 160, 400, or 1000μM phosphorus (P) to investigate the effects of P supply on root citrate and malate release, the concentrations of malate and citrate and the activities of acid-metabolizing enzymes in leaves and roots. Root malate release and accumulation was induced by both 0 and 40μM P, while root citrate release and accumulation was induced only by 0μM P. Phosphorus-deficiency-induced malate and citrate release coincided with higher concentrations of root malate and citrate. The higher concentrations of malate and citrate were accompanied by increased activities of phosphoenolpyruvate carboxylase (PEPC), phosphoenolpyruvate phosphatase (PEPP), citrate synthase (CS) and NAD-malic enzyme (NAD-ME) and decreased activities of pyruvate kinase (PK), NADP-ME and NADP-isocitrate dehydrogenase (NADP-IDH) in roots. In contrast to roots, malate accumulated in the leaves only in response to 0μM P, and no change was observed in citrate levels. The P-deficiency-induced leaf malate accumulation coincided with increased activities of NADP-ME, NAD-ME and PK. Overall, the P-deficiency-induced changes in organic acid (OA) metabolism differed between roots and leaves. The high tolerance of tea plants to P-deficiency might be involved in two major processes: (a) increasing the availability of P by inducing root release of OA anions; and (b) improving the ability to use P efficiently by inducing bypass enzymes involved in tissue P economy.

Seedlings of sour pummelo (Citrus grandis) were irrigated daily for 18 weeks with nutrient solution containing four phosphorus (P) levels (50, 100, 250 and 500 microM KH2PO4) and two aluminum (Al) levels [0 (-Al) and 1.2 mM AlCl3 x 6H2O (+Al)]. Both malate and citrate concentrations in +Al leaves decreased with increasing P supply, but their concentrations in -Al leaves did not change in response to P supply. The concentrations of malate under 50 microM P and of citrate under 50 and 100 microM P were higher in +Al leaves than in -Al ones, but malate concentration was lower in +Al leaves than in -Al ones under 500 microM P. There was no difference in root malate and citrate concentrations among different P and Al combinations except for an increase in malate and citrate under 50 microM P+0 mM Al and a slight decrease in malate under 50 microM P+1.2 mM Al. The activities of acid-metabolizing enzymes (citrate synthase, aconitase, phosphoenolpyruvate carboxylase, NADP-isocitrate dehydrogenase, phosphoenolpyruvate phosphatase, NAD-malate dehydrogenase, NADP-malic enzyme and pyruvate kinase) in most cases were less affected by P and Al interactions in roots compared to the leaves. Our results support the hypothesis that changes in organic acid metabolism differ between roots and leaves of C. grandis in response to P and Al interactions.

Seedlings of Citrus grandis (L.) Osbeck cv. Tuyou were irrigated daily for 5 months with nutrient solution containing 0 (control), 0.2, 0.6 or 1.6 mM aluminum (Al) from AlCl(3).6H(2)O. Shoot growth was more sensitive to Al toxicity than root growth, gas exchange, chlorophyll (Chl) concentration, polyphasic Chl a fluorescence (OJIP) induction and related parameters. Leaves of Al-treated plants showed decreased CO(2) assimilation and Chl concentration, yet intercellular CO(2) concentration increased and ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) activity was unchanged. Chlorophyll a fluorescence induction analysis of Al-stressed leaves showed a large rise at the O-step and a large depression at the P-step, accompanied by two new bands at 300 micros (K-band) and at about 150 micros (L-band). Maximum fluorescence, maximum quantum yield of primary photochemistry, oxygen-evolving complex (OEC), quantum yield of electron transport, quantum yield of electron transport from Q(A) (-) to the Photosystem I end electron acceptors, IP phase and total performance index were decreased in leaves of Al-treated plants, whereas minimum fluorescence, relative variable fluorescence at the J-step and I-step, and dissipated energy were increased. We propose that impaired electron transport capacity accompanied by lack of reducing equivalents were the main factors contributing to decreased CO(2) assimilation in Al-treated plants. Aluminum-induced photoinhibition occurring at both the donor (i.e., the OEC) and the acceptor sides of Photosystem II may be associated with growth inhibition. Besides decreased light absorption due to reduced Chl concentration, enhanced energy dissipation protected the leaves of Al-treated plants from photo-oxidative damage in high light.

Own-rooted one-year-old `Concord' grapevines were fertigated twice weekly for 11 weeks with 1, 10, 20, 50, OR 100 μmol iron (Fe) from ferric ethylenediamine di (o-hydroxyphenylacetic) acid in a complete nutrient solution. As Fe supply increased, leaf total Fe content did not change, whereas active Fe (extracted by 2, 2'-dipyridyl) and total chlorophyll content increased curvilinearly. CO2 assimilation and stomatal conductance increased curvilinearly with increasing active Fe, whereas intercellular CO2 concentrations decreased linearly. Activities of key Calvin cycle enzymes, Rubisco, NADP-glyceraldehyde-3-phosphate dehydrogenase, phosphoribulokinase, stromal fructose-1,6-bisphosphatase (FBPase), and a key enzyme in sucrose synthesis, cytosolic FBPase, all increased linearly with increasing active Fe. No difference was found in the activities of ADP-glucose pyrophosphorylase and sucrose phosphate synthase of leaves between the lowest and the highest treatments, whereas slightly lower activities were observed in the middle Fe treatments. Content of 3-phosphoglycerate increased curvilinearly with increased active Fe, whereas glucose-6-phosphate and fructose-6-phosphate did not change. Glucose, fructose, sucrose, starch, and total non-structural carbohydrates at both dusk and pre-dawn increased with increasing active Fe. Carbon export from starch breakdown during the night, calculated as the difference between dusk and predawn levels, increased as active Fe increased. In conclusion, Fe limitation reduces the activities of Rubisco and other photosynthetic enzymes, and hence CO2 assimilation capacity. Fe-deficient grapevines have lower concentrations of non-structural carbohydrates in source leaves, and therefore, are source limited.

Plants grown on calcareous soils often exhibit symptoms of Fe-deficiency induced chlorosis despite a high content of total Fe in the leaf tissue. Iron is transported in the xylem primarily as the ferric citrate (Fe-Citr) chelate, and changes in pH, HCO -3, and Citr can lead to the formation of different Fe-Citr species. Understanding how Fe dissociates from these chelates may help explain why Fe is immobilized in the leaves. The goal was to quantify Fe mobilization (Fe-Mob) from Fe-Citr in an assay system buffered at pH 5, 6, or 7 when: 1) the molar ratio of HCO -3 to Fe increased in a 1 Fe: 1 Citr system; 2) the molar ratio of Citr increased in a 1 Fe: 3 HCO -3 system; and 3) solutions were photoreduced (PR) or left in the dark. For non-PR solutions, Fe-Mob from Fe-Citr using 500 μmol NADH was the greatest at the 1 Fe: 0 HCO -3-level, and decreased as HCO -3 increased. Fe-Mob also decreased as buffer pH increased from 5 to 7. Increasing the Citr ratio was effective in increasing Fe-Mob, but the effect decreased as buffer pH increased from 5 to 7. PR solutions behaved quite differently. In the 1 Fe: 1 Citr system, little to no Fe-Mob was detected at any buffer pH. However, there were already large pools of Fe2+ in solution, which decreased as HCO -3 increased, irrespective of buffer pH. Increasing the Citr ratio greatly increased Fe-Mob in the 1 Fe: 3 HCO -3 system, and mobilization decreased as buffer pH increased. Increasing Citr did not increase the amount of Fe2+ in solution. This work illustrates that increasing the HCO -3: Fe ratio can lead to an immobilization of Fe, and that increasing the Citr ratio can aid in Fe-Mob from Fe-Citr when the HCO -3: Fe ratio is high. Increasing the Citr ratio, however, does not increase the amount of PR Fe2+.

One-year-old `Concord' grapevines (Vitis labrusca L.) were fertigated twice weekly for 11 weeks with a complete nutrient solution containing 1, 10, 20, 50 or 100 μmol iron (Fe) from ferric ethylenediamine di (o-hydroxyphenylacetic) acid (Fe-EDDHA). Leaf total Fe content did not increase in response to Fe supply, however both “active” Fe (extracted with 2, 2'-dipyridyl) and chlorophyll (Chl) content increased as applied Fe increased. At the lowest active Fe level, leaf absorptance and maximum PSII efficiency (Fv/Fm) were slightly decreased, and non-photochemical quenching was significantly greater. PSII quantum efficiency decreased curvilinearly as active Fe content decreased. On a Chl basis, the xanthophyll cycle pool size, lutein, and beta-carotene increased curvilinearly as active Fe decreased, and neoxanthin increased at the lowest Fe level. Activities of antioxidant enzymes superoxide dismutase, ascorbate peroxidase, monodehydroascorbate reductase, dehydroascorbate reductase, and glutathione reductase followed a similar trend and increased under Fe deficiency, when expressed on a Chl basis. Antioxidant metabolites also increased in response to Fe limitation. On a Chl basis, ascorbate (AsA), dehydroascorbate (DAsA), reduced glutathione (GSH) and oxidized glutathione (GSSG) content was greater at the lowest active Fe levels. We did not find a difference in the ratio of AsA to DAsA or GSH to GSSG. In conclusion, both photoprotective mechanisms, xanthophyll cyle-dependent thermal dissipation and the ascorbate-glutatione antioxidant system, are enhanced in response to iron deficiency to cope with excess absorbed light.