A Self-Assembled Cage for Wide-Scope Chiral Recognition in Water.

Herein, we report the self-assembly of an anionic homochiral octahedral cage by condensing six Ga3+ cations and four trisacylhydrazone ligands. The robust nature of the hydrazone bond renders the cage stable in water, where it can take advantage of the hydrophobic effect for host-guest recognition. In addition to the internal binding site, namely, the inner cavity, the octahedral cage possesses four "windows", each of which represents an external binding site allowing peripheral complexation. These internal and external binding sites endow the cage with the capability to bind a broad range of guests whose sizes could either be smaller than or exceed the volume of the cage's inner cavity. Upon accommodation of a chiral guest, one of the two cage enantiomers becomes more favored than the other, producing circular-dichroism (CD) signals. The CD signal intensity of the cage is observed to be proportional to the ee value of the chiral guest, allowing a quantitative determination of the latter.

Self-Assembly in Water with N-Substituted Imines.

Imine synthesis has enjoyed a long history as the dynamic covalent reaction of choice for the construction of purely covalent molecular architectures. In organic solvents, the formation of imine bonds is reversible but leads to thermodynamically stable products. In the presence of water, however, imine bonds are labile, a fact which limits their utility as mediators of self-assembly in aqueous and biological media. In this Review, we discuss water-compatible dynamic covalent bonds based on N-substituted imine derivatives, namely hydrazones and oximes, for the self-assembly of metal-free organic architectures with well-defined structures. The reasons why hydrazones and oximes are more robust in water than their parent imines are explained. Recent progress in the self-assembly, characterization, and design principles of a variety of complex molecules including macrocycles, cages, catenanes, and knots in aqueous media is highlighted. Emerging applications for these molecules, including guest recognition and separations, are also discussed.

Dynamic Covalent Self-Assembly Based on Oxime Condensation.

Oxime, whose dynamic nature was reported to be switchable between ON/OFF by tuning the acidity, is employed in a novel type of dynamic covalent approach that is amenable to use in water for self-assembly of purely organic molecules with complex topology. In strongly acidic conditions, the dynamic nature of oxime is turned ON, allowing occurrence of error-checking and therefore a catenane and a macrocycle self-assembled in high yields. In neutral conditions, oxime ceases to be dynamic, which helps to trap the self-assembled products even when the driving forces of their formation are removed. We envision that this switchable behaviour might help, at least partially, to resolve a commonly encountered drawback of dynamic covalent chemistry, namely that the intrinsic stability of the self-assembled products containing dynamic bonds, such as imine or hydrazone, are often jeopardized by their reversible nature.

Effects of water management on arsenic and cadmium speciation and accumulation in an upland rice cultivar.

Pot and field experiments were conducted to investigate the effects of water regimes on the speciation and accumulation of arsenic (As) and cadmium (Cd) in Brazilian upland rice growing in soils polluted with both As and Cd. In the pot experiment constant and intermittent flooding treatments gave 3-16 times higher As concentrations in soil solution than did aerobic conditions but Cd showed the opposite trend. Compared to arsenate, there were more marked changes in the arsenite concentrations in the soil solution as water management shifted, and therefore arsenite concentrations dominated the As speciation and bioavailability in the soil. In the field experiment As concentrations in the rice grains increased from 0.14 to 0.21 mg/kg while Cd concentrations decreased from 0.21 to 0.02 mg/kg with increasing irrigation ranging from aerobic to constantly flooding conditions. Among the various water regimes the conventional irrigation treatment produced the highest rice grain yield of 6.29 tons/ha. The As speciation analysis reveals that the accumulation of dimethylarsinic acid (from 11.3% to 61.7%) made a greater contribution to the increase in total As in brown rice in the intermittent and constant flooding treatments compared to the intermittent-aerobic treatment. Thus, water management exerted opposite effects on Cd and As speciation and bioavailability in the soil and consequently on their accumulation in the upland rice. Special care is required when irrigation regime methods are employed to mitigate the accumulation of metal(loid)s in the grain of rice grown in soils polluted with both As and Cd.

Multinomial machine learning identifies independent biomarkers by integrated metabolic analysis of acute coronary syndrome.

A multi-class classification model for acute coronary syndrome (ACS) remains to be constructed based on multi-fluid metabolomics. Major confounders may exert spurious effects on the relationship between metabolism and ACS. The study aims to identify an independent biomarker panel for the multiclassification of HC, UA, and AMI by integrating serum and urinary metabolomics. We performed a liquid chromatography-tandem mass spectrometry (LC-MS/MS)-based metabolomics study on 300 serum and urine samples from 44 patients with unstable angina (UA), 77 with acute myocardial infarction (AMI), and 29 healthy controls (HC). Multinomial machine learning approaches, including multinomial adaptive least absolute shrinkage and selection operator (LASSO) regression and random forest (RF), and assessment of the confounders were applied to integrate a multi-class classification biomarker panel for HC, UA and AMI. Different metabolic landscapes were portrayed during the transition from HC to UA and then to AMI. Glycerophospholipid metabolism and arginine biosynthesis were predominant during the progression from HC to UA and then to AMI. The multiclass metabolic diagnostic model (MDM) dependent on ACS, including 2-ketobutyric acid, LysoPC(18:2(9Z,12Z)), argininosuccinic acid, and cyclic GMP, demarcated HC, UA, and AMI, providing a C-index of 0.84 (HC vs. UA), 0.98 (HC vs. AMI), and 0.89 (UA vs. AMI). The diagnostic value of MDM largely derives from the contribution of 2-ketobutyric acid, and LysoPC(18:2(9Z,12Z)) in serum. Higher 2-ketobutyric acid and cyclic GMP levels were positively correlated with ACS risk and atherosclerosis plaque burden, while LysoPC(18:2(9Z,12Z)) and argininosuccinic acid showed the reverse relationship. An independent multiclass biomarker panel for HC, UA, and AMI was constructed using the multinomial machine learning methods based on serum and urinary metabolite signatures.

Selective Recognition of Chloride Anion in Water.

A tricationic cage was synthesized via click chemistry. The cage has a preorganized cavity, which is surrounded by six relatively acidic C-H bonds. In organic solvent, the cage can recognize a variety of anions, among which the Cl- anion has the highest binding affinity due to size selectivity. The cage is also able to selectively recognize the Cl- anion in water, even though the binding affinity is just moderate.

A mutually stabilized host-guest pair.

By using click chemistry, a hexacationic cage was synthesized. The cage contains two triscationic π-electron-deficient trispyridiniumtriazine (TPZ3+) platforms that are bridged in a face-to-face manner by three ethylene-triazole-ethylene linkers. A diversity of π-electron-rich guests can be recognized within the pocket of the cage, driven by host-guest π-π interactions. The cage cavity acts as a protecting group, preventing an anthracene guest from undergoing Diels-Alder reaction. Under ultraviolet (UV) light, the pyridinium C─N bonds in TPZ3+ platforms are polarized and weakened, resulting in the occurrence of cage decomposition via ß-elimination. Guest recognition could help to prevent this UV-stimulated cage decomposition by suppressing the excitation of the TPZ3+ units.

Guest recognition enhanced by lateral interactions.

A hexacationic triangular covalent organic cage, AzaEx2Cage 6+, has been synthesized by means of a tetrabutylammonium iodide-catalyzed SN2 reaction. The prismatic cage is composed of two triangular 2,4,6-triphenyl-1,3,5-triazine (TPT) platforms bridged face-to-face by three 4,4'-bipyridinium (BIPY 2+) spacers. The rigidity of these building blocks leads to a shape-persistent cage cavity with an inter-platform distance of approximately 11.0 Å. This distance allows the cage to accommodate two aromatic guests, each of which is able to undergo π-π interactions with one of the two TPT platform simultaneously, in an A-D-D-A manner. In the previously reported prism-shaped cage, the spacers (pillars) are often considered passive or non-interactive. In the current system, the three BIPY 2+ spacers are observed to play an important role in guest recognition. Firstly, the BIPY 2+ spacers are able to interact with the carbonyl group in a pyrene-1-carbaldehyde (PCA) guest, by introducing lateral dipole-cation or dipole-dipole interactions. As a consequence, the binding affinity of the cage towards the PCA guest is significantly larger than that of pyrene as the guest, even although the latter is often considered to be a better π-electron donor. Secondly, in the case of the guest 1,5-bis[2-(2-(2-(2-hydroxyethoxy)ethoxy)ethoxy)ethoxy]naphthalene (BH4EN), the pillars can provide higher binding forces compared to the TPT platform. Hence, peripheral complexation occurs when AzaEx2Cage 6+ accommodates BH4EN in MeCN. Thirdly, when both PCA and BH4EN are added into a solution of AzaEx2Cage 6+, inclusion and peripheral complexation occur simultaneously to PCA and BH4EN respectively, even though the accommodation of the former guest seems to attenuate the external binding of the latter. This discovery of the importance of lateral interactions highlights the relationship between the electrostatic properties of a highly charged host and its complexation behavior, and as such, provides insight into the design of more complex hosts that bind guests in multiple locations and modes.

A diquat-containing macrocyclic anion acceptor in pure water.

By taking advantage of a newly developed self-assembly approach based on oxime condensation, we successfully obtained a tetracationic macrocycle bearing two diquats in acidic aqueous media in a high yield. The ring is able to accommodate HPO42- and HCO3- in pure water.

Precursor control over the self-assembly of [2]catenanes via hydrazone condensation in water.

By means of hydrazone condensation, a series of homo-[2]catenanes were self-assembled in high yields in water. The properties of the precursors have a great impact on the self-assembly pathway, as well as the stability and co-conformations of the products.

[Effects of intercropping Sedum plumbizincicola in wheat growth season under wheat-rice rotation on the crops growth and their heavy metals uptake from different soil types].

A pot experiment with heavy metals- contaminated black soil from Heilongjiang Province, alluvial soil from Henan Province, and paddy soil from Zhejiang Province was conducted to study the effects of intercropping Sedum plumbizincicola in wheat growth season under wheat (Triticum aestivum) - rice (Oryza sativa) rotation on the growth of the crops and their heavy metals uptake, aimed to explore the feasibility of simultaneous grain production and heavy metals-contaminated soil phytoremediation in main food crop production areas of this country. Comparing with monoculture T. aestivum, intercropping S. plumbizincicola increased the soil NaNO3 -extractable Zn and Cd significantly, with the increment of extractable Zn in test paddy soil, alluvial soil, and black soil being 55%, 32% and 110%, and that of extractable Cd in test paddy soil and black soil being 38% and 110%, respectively. The heavy metals concentration in T. aestivum shoots under intercropping S. plumbizincicola was 0.1-0.9 times higher than that under monoculture T. aestivum, but the intercropping had little effects on the rice growth and its heavy metals uptake. Though the Cd concentration in rice grain after S. plumbizincicola planting was still higher than 0.2 mg kg(-1) (the limit of Cd in food standard), it presented a decreasing trend, as compared with that after monoculture T. aestivum. Therefore, intercropping S. plumbizincicola in wheat growth season under wheat-rice rota- tion could benefit the phytoremediation of heavy metals-contaminated soil, and decrease the food-chain risk of rotated rice.

[Effects of Sedum plumbizincicola--Oryza sativa rotation and phosphate amendment on Cd and Zn uptake by O. sativa].

In a pot experiment, hyperaccumulator Sedum plumbizincicola and low-cadmium accumulating Oryza sativa cultivar "Zhongxiang No. 1" were planted in rotation on a heavy metals-polluted soil, and calcium magnesium phosphate (Ca-P) and rock phosphate (P-R) were amended, aimed to study the effects of the rotation and phosphate amendment on the growth of the two plants and the zinc- and cadmium accumulation in their shoots. After the amendment of 50 g P-R x kg(-1), the Zn and Cd uptake by S. plumbizincicola was 11.5 mg x pot(-1) and 0 x 79 mg x pot(-1), respectively, being significantly higher than that after the amendment of 4 g Ca-P x kg(-1). After the planting of S. plumbizincicola, the Zn and Cd concentrations in "Zhongxiang No. 1" increased, but the amendment of Ca-P decreased the accumulation of Zn and Cd in rice shoot significantly. The rotation with S. plumbizincicola and the amendment of Ca-P and P-R could immobilize the Zn and Cd in the contaminated soil as indicated by the quantitative change of NH4OAc-extractable Cd and Zn, and the efficiency of amendment with Ca-P was better than that of amendment with P-R. Field trial showed that amendment with Ca-P could not only increase the rice yield, but also reduce the Zn and Cd accumulation in rice shoot to a certain extent.