Modular and predictable assembly of porous organic molecular crystals

Nanoporous molecular frameworks are important in applications such as separation, storage and catalysis. Empirical rules exist for their assembly but it is still challenging to place and segregate functionality in three-dimensional porous solids in a predictable way. Indeed, recent studies of mixed crystalline frameworks suggest a preference for the statistical distribution of functionalities throughout the pores rather than, for example, the functional group localization found in the reactive sites of enzymes. This is a potential limitation for 'one-pot' chemical syntheses of porous frameworks from simple starting materials. An alternative strategy is to prepare porous solids from synthetically preorganized molecular pores. In principle, functional organic pore modules could be covalently prefabricated and then assembled to produce materials with specific properties. However, this vision of mix-and-match assembly is far from being realized, not least because of the challenge in reliably predicting three-dimensional structures for molecular crystals, which lack the strong directional bonding found in networks. Here we show that highly porous crystalline solids can be produced by mixing different organic cage modules that self-assemble by means of chiral recognition. The structures of the resulting materials can be predicted computationally, allowing in silico materials design strategies. The constituent pore modules are synthesized in high yields on gram scales in a one-step reaction. Assembly of the porous co-crystals is as simple as combining the modules in solution and removing the solvent. In some cases, the chiral recognition between modules can be exploited to produce porous organic nanoparticles. We show that the method is valid for four different cage modules and can in principle be generalized in a computationally predictable manner based on a lock-and-key assembly between modules

Blood pressure variability and cardiovascular risk in the PROspective study of pravastatin in the elderly at risk (PROSPER)

Variability in blood pressure predicts cardiovascular disease in young- and middle-aged subjects, but relevant data for older individuals are sparse. We analysed data from the PROspective Study of Pravastatin in the Elderly at Risk (PROSPER) study of 5804 participants aged 70–82 years with a history of, or risk factors for cardiovascular disease. Visit-to-visit variability in blood pressure (standard deviation) was determined using a minimum of five measurements over 1 year; an inception cohort of 4819 subjects had subsequent in-trial 3 years follow-up; longer-term follow-up (mean 7.1 years) was available for 1808 subjects. Higher systolic blood pressure variability independently predicted long-term follow-up vascular and total mortality (hazard ratio per 5 mmHg increase in standard deviation of systolic blood pressure = 1.2, 95% confidence interval 1.1–1.4; hazard ratio 1.1, 95% confidence interval 1.1–1.2, respectively). Variability in diastolic blood pressure associated with increased risk for coronary events (hazard ratio 1.5, 95% confidence interval 1.2–1.8 for each 5 mmHg increase), heart failure hospitalisation (hazard ratio 1.4, 95% confidence interval 1.1–1.8) and vascular (hazard ratio 1.4, 95% confidence interval 1.1–1.7) and total mortality (hazard ratio 1.3, 95% confidence interval 1.1–1.5), all in long-term follow-up. Pulse pressure variability was associated with increased stroke risk (hazard ratio 1.2, 95% confidence interval 1.0–1.4 for each 5 mmHg increase), vascular mortality (hazard ratio 1.2, 95% confidence interval 1.0–1.3) and total mortality (hazard ratio 1.1, 95% confidence interval 1.0–1.2), all in long-term follow-up. All associations were independent of respective mean blood pressure levels, age, gender, in-trial treatment group (pravastatin or placebo) and prior vascular disease and cardiovascular disease risk factors. Our observations suggest variability in diastolic blood pressure is more strongly associated with vascular or total mortality than is systolic pressure variability in older high-risk subjects

Stress-induced amorphization at moving crack tips in NiTi

In situ fracture studies on thin-film NiTi intermetallic compounds have been carried out in the high-voltage electron microscope at Argonne National Laboratory. Local stress-induced amorphization of regions directly in front of moving crack tips has been observed under tensile loading conditions. The stress-induced amorphization at crack tips exhibits a temperature dependence similar to that of ion-induced amorphization of NiTi. The upper limiting temperature for stress-induced amorphization is the same as that for ion-induced amorphization of crystalline NiTi and for amorphous phase formation during ion-beam mixing of Ni and Ti multilayer specimens. This upper limiting temperature of 600K is also the lowest temperature at which stress-induced amorphous phase crystallizes during isothermal annealing. This isothermal crystallization temperature is nearly 200K less than the kinetic crystallization temperature during heating of unrelaxed NiTi glasses formed by rapid quenching or vapor phase deposition

Increased glutamine in leaves of poplar transgenic with pine GS1a caused greater anthranilate synthetase α-subunit (ASA1) transcript and protein abundances: an auxin-related mechanism for enhanced growth in GS transgenics?

The initial reaction in the pathway leading to the production of indole-3-acetic acid (IAA) in plants is the reaction between chorismate and glutamine to produce anthranilate, catalysed by the enzyme anthranilate synthase (ASA; EC 4.1.3.27). Compared with non-transgenic controls, leaves of transgenic poplar with ectopic expression of the pine cytosolic glutamine synthetase (GS1a; EC 6.3.1.2) produced significantly greater glutamine and significantly enhanced ASA α-subunit (ASA1) transcript and protein (approximately 130% and 120% higher than in the untransformed controls, respectively). Similarly, tobacco leaves fed with 30 mM glutamine and 2 mM chorismate showed enhanced ASA1 transcript and protein (175% and 90% higher than controls, respectively). Furthermore, free IAA was significantly elevated both in leaves of GS1a transgenic poplar and in tobacco leaves fed with 30 mM glutamine and 2 mM chorismate. These results indicated that enhanced cellular glutamine may account for the enhanced growth in GS transgenic poplars through the regulation of auxin biosynthesis

Significant nutrient consumption in the dark subsurface layer during a diatom bloom: a case study on Funka Bay, Hokkaido, Japan

We conducted repetitive observations in Funka Bay, Hokkaido, Japan, on 15 February, 4 and 15 March, and 14 April 2019. The diatom spring bloom peaked on 4 March and started declining on 15 March. Funka Bay winter water remained below 30 m depth, which was below the surface mixed-layer and dark-layer depth (0.1 % of the surface photosynthetically active radiation, PAR, depth) on 4 and 15 March. In the subsurface layer at depths of 30–50 m, concentrations of NO3-, PO43-, and Si(OH)4 decreased by half between these dates, even in the dark. Incubation experiments using the diatom Thalassiosira nordenskioeldii showed that this diatom could consume added nutrients in the dark at substantial rates after pre-culturing to deplete nutrients. Incubation experiments using natural seawater collected in the growing phase of the bloom on 8 March 2022 also showed that nutrient-depleted phytoplankton could consume added nutrients in the dark. We excluded three physical process – water mixing, diffusive transport, and subduction – as possible main reasons for the decrease in nutrients in the subsurface layer. We conclude that the nutrient reduction in the subsurface layer (30–50 m) between 4 and 15 March 2019 could be explained by nutrient consumption by diatoms in the dark in that layer.</p

Association between asymptomatic hyperuricemia and new-onset chronic kidney disease in Japanese male workers: a long-term retrospective cohort study

<p>Abstract</p> <p>Background</p> <p>Hyperuricemia is prevalent in patients with chronic kidney disease (CKD). We explored the hypothesis that asymptmatic hyperuricemia may be associated with new-onset CKD.</p> <p>Methods</p> <p>The participants were all male factory workers in Kanagawa, Japan (n = 1,285). All were over 40 years of age and had undergone annual health examinations from 1990 to 2007. Individuals with a history of gouty attacks were excluded from the study. A retrospective cohort study was conducted by following the estimated glomerular filtration rate (eGFR) for each participant over a maximum period of 18 years. The endpoint was new-onset CKD defined as eGFR < 60 mL/min/1.73 m². The associations between new-onset CKD and the presence of hyperuricemia, low serum high-density lipoprotein cholesterol, hypertension, diabetes, and obesity were analyzed.</p> <p>Results</p> <p>The mean (± standard deviation) follow-up period was 95.2 (± 66.7) months, and new-onset CKD was observed in 100 participants (7.8%) during this follow-up. Cox proportional hazards model revealed that the hazard ratio of new-onset CKD due to hyperuricemia, low serum high-density lipoprotein cholesterol, hypertension and obesity were 3.99 (95% confidence interval: 2.59-6.15), 1.69 (1.00-2.86), 2.00 (1.29-3.11) and 1.35 (0.87-2.10), respectively. Concerning hyperuricemia, low serum high-density lipoprotein cholesterol, hypertension and obesity, the log-rank tests showed <it>P </it>values of < 0.01, 0.01, < 0.01 and < 0.01, respectively.</p> <p>Conclusion</p> <p>The results of this study suggest that asymptomatic hyperuricemia is a predictive factor for new-onset CKD for Japanese male workers.</p