Temperature-Dependent Separation of CO2 from Light Hydrocarbons in a Porous Self-Assembly of Vertexes Sharing Octahedra.

Design of flexible porous materials where the diffusion of guest molecules is regulated by the dynamics of contracted pore aperture is challenging. Here, a flexible porous self-assembly consisting of 1D channels with dynamic bottleneck gates is reported. The dynamic pendant naphthimidazolylmethyl moieties at the channel necks provide kinetic gate function, that enables unusual adsorption for light hydrocarbons. The adsorption for CO2 is mainly dominated by thermodynamics with the uptakes decreasing with increasing temperature, whereas the adsorptions for larger hydrocarbons are controlled by both thermodynamics and kinetics resulting in an uptake maximum at a temperature threshold. Such an unusual adsorption enables temperature-dependent separation of CO2 from the corresponding hydrocarbons.

Responsible genes in children with primary vesicoureteral reflux: findings from the Chinese Children Genetic Kidney Disease Database.

BACKGROUND: Primary vesicoureteral reflux (VUR) is a common congenital anomaly of the kidney and urinary tract (CAKUT) in childhood. The present study identified the possible genetic contributions to primary VUR in children. METHODS: Patients with primary VUR were enrolled and analysed based on a national multi-center registration network (Chinese Children Genetic Kidney Disease Database, CCGKDD) that covered 23 different provinces/regions in China from 2014 to 2019. Genetic causes were sought using whole-exome sequencing (WES) or targeted-exome sequencing. RESULTS: A total of 379 unrelated patients (male: female 219:160) with primary VUR were recruited. Sixty-four (16.9%) children had extrarenal manifestations, and 165 (43.5%) patients showed the coexistence of other CAKUT phenotypes. Eighty-eight patient (23.2%) exhibited impaired renal function at their last visit, and 18 of them (20.5%) developed ESRD at the median age of 7.0 (IQR 0.9-11.4) years. A monogenic cause was identified in 28 patients (7.39%). These genes included PAX2 (n = 4), TNXB (n = 3), GATA3 (n = 3), SLIT2 (n = 3), ROBO2 (n = 2), TBX18 (n = 2), and the other 11 genes (one gene for each patient). There was a significant difference in the rate of gene mutations between patients with or without extrarenal complications (14.1% vs. 6%, P = 0.035). The frequency of genetic abnormality was not statistically significant based on the coexistence of another CAKUT (9.6% vs. 5.6%, P = 0.139, Chi-square test) and the grade of reflux (9.4% vs. 6.7%, P = 0.429). Kaplan-Meier survival curve showed that the presence of genetic mutations did affect renal survival (Log-rank test, P = 0.01). PAX2 mutation carriers (HR 5.1, 95% CI 1.3-20.0; P = 0.02) and TNXB mutation carriers (HR 20.3, 95% CI 2.4-168.7; P = 0.01) were associated with increased risk of progression to ESRD. CONCLUSIONS: PAX2, TNXB, GATA3 and SLIT2 were the main underlying monogenic causes and accounted for up to 46.4% of monogenic VUR. Extrarenal complications and renal function were significantly related to the findings of genetic factors in children with primary VUR. Like other types of CAKUT, several genes may be responsible for isolated VUR.

[Study on suitable distribution areas of Sichuan safflower in Sichuan province based on 3S technologies].

Sichuan safflower (Carthamus tinctorius) is a traditional Chinese medicine for promoting blood circulation and removing blood stasis. In this paper, taking Sichuan province as an example, based on TM image, digital elevation model (DEM), meteorology, soil and other data, and using remote sensing and GIS technology to extract grassland, elevation, temperature and precipitation, soil and other influencing factors, the spatial distribution of the suitability of safflower was studied, and the field investigation was carried out. The results indicate that Sichuan safflower resources are mainly concentrated in the eastern and northeastern parts of Sichuan, and the suitable distribution area is about 6 277.14 km2. The area of suitable area of Dazhou is 1 143.45 km², which is suitable for the province area of 18.22%. From the county point of view, the suitable area of Dachuan is about 507.15 km², and accounting for 17.9% of county. In addition, Naxi, Qingshen, Jiangan and other 12 counties of the suitable area of more than 100 km², and accounted for more than 10% of the county. The results of remote sensing and GIS analysis are in accordance with the real area of Sichuan safflower resources. It is feasible to find out the area suitable for the growth of Sichuan safflower by 3S technologies. It can provide a scientific basis for the monitoring and development of Chinese herbal resources.

Selective CO2 Capture and High Proton Conductivity of a Functional Star-of-David Catenane Metal-Organic Framework.

Network structures based on Star-of-David catenanes with multiple superior functionalities have been so far elusive, although numerous topologically interesting networks are synthesized. Here, a metal-organic framework featuring fused Star-of-David catenanes is reported. Two triangular metallacycles with opposite handedness are triply intertwined forming a Star-of-David catenane. Each catenane fuses with its six neighbors to generate a porous twofold intercatenated gyroid framework. The compound possesses exceptional stability and exhibits multiple functionalities including highly selective CO2 capture, high proton conductivity, and coexistence of slow magnetic relaxation and long-range ordering.

[Predictive distribution and planting GAP of Cyathula officinalis in China based on 3S technology and MaxEnt modelling].

Research on predictive distribution and planting GAP of Cyathula officinalis in China is helpful to provide scientific basis for its protection and planting popularization. According to the data in 63 distribution sites and 49 ecological variables, using MaxEnt ecological niche model and 3S technology, we performed a quantitative analysis of suitable distribution and planting GAP of C. officinalis in China. Our results show that: ① the area of suitable distribution of C. officinalis is about 634 385.80 km² in total, and mainly in Northeastern and Southeastern Sichuan, Northern and Southeastern Yunnan, Western and Southwestern Guizhou, Southwestern and Northeastern Chongqing, Southwestern Shaanxi, Southeastern Gansu, Western Guangxi, Southeastern Tibet. ② The main ecological factors determining the potential distribution are precipitation, altitude, minimum temperature of coldest month, soil type, monthly mean temperature. ③ The planting GAP region are mainly in Guangyuan, Mianyang, Ya'an, Leshan, Liangshan, Panzhihua of Sichuan province, Hanzhong of Shaanxi province, Dali, Nujiang, Chuxiong, Baoshan, Qujing, Wenshan of Yunnan province, southwestern autonomous prefecture in Guizhou province. The results are of great significance for realizing the growth environment, predicting the potential distribution and promoting planting popularization for C. officinalis.

Superior thermoelasticity and shape-memory nanopores in a porous supramolecular organic framework.

Flexible porous materials generally switch their structures in response to guest removal or incorporation. However, the design of porous materials with empty shape-switchable pores remains a formidable challenge. Here, we demonstrate that the structural transition between an empty orthorhombic phase and an empty tetragonal phase in a flexible porous dodecatuple intercatenated supramolecular organic framework can be controlled cooperatively through guest incorporation and thermal treatment, thus inducing empty shape-memory nanopores. Moreover, the empty orthorhombic phase was observed to exhibit superior thermoelasticity, and the molecular-scale structural mobility could be transmitted to a macroscopic crystal shape change. The driving force of the shape-memory behaviour was elucidated in terms of potential energy. These two interconvertible empty phases with different pore shapes, that is, the orthorhombic phase with rectangular pores and the tetragonal phase with square pores, completely reject or weakly adsorb N2 at 77 K, respectively.

Magnetic Properties of 3D Heptanuclear Lanthanide Frameworks Supported by Mixed Ligands.

Two 3D lanthanide frameworks, [Ln7(DPA)5(NA)3(µ3-OH)8(H2O)3]·2.5H2O [H2DPA = diphenic acid; HNA = nicotinic acid; Ln = Gd (1), Dy (2)], were synthesized and structurally characterized. They were rarely seen examples of 3D frameworks constructed from heptanuclear trigonal-antiprismatic lanthanide clusters with mixed H2DPA and HNA ligands. Both 1 and 2 show typical antiferromagnetic interactions. Additionally, complex 1 possesses a large magnetocaloric effect of 34.15 J kg(-1) K(-1).

Construction of two microporous metal-organic frameworks with flu and pyr topologies based on Zn4(µ3-OH)2(CO2)6 and Zn6(µ6-O)(CO2)6 secondary building units.

By employment of a tripodal phosphoric carboxylate ligand, tris(4-carboxylphenyl)phosphine oxide (H3TPO), two novel porous metal-organic frameworks, namely, [Zn4(µ3-OH)2(TPO)2(H2O)2] (1) and [Zn6(µ6-O)(TPO)2](NO3)4·3H2O (2), have been synthesized by solvothermal methods. Complexes 1 and 2 exhibit three-dimensional microporous frameworks with flu and pyr topologies and possess rare butterfly-shaped Zn4(µ3-OH)2(CO2)6 and octahedral Zn6(µ6-O)(CO2)6 secondary building units, respectively. Large cavities and one-dimensional channels are observed in these two frameworks. Gas-sorption measurements indicate that complex 2 has a good H2 uptake capacity of 171.9 cm(3) g(-1) (1.53 wt %) at 77 K and 1.08 bar, and its ideal adsorbed solution theory calculation predicts highly selective adsorption of CO2 over N2 and CH4. Furthermore, complexes 1 and 2 exhibit excellent blue emission at room temperature.

A solid AND logic stimuli-responsive material with bright nondestructive performance designed by sensitive cuprophilicity.

A stimuli-responsive material with AND logic function was realized by modulating sensitive Cu-Cu interactions, which is quite different from traditional photoinduced electron transfer (PET) strategies. The obtained material not only gets rid of fluid media, but also displays nondestructive, high intensity optical signals and environmentally friendly performances.

A series of novel zinc(II) entangled coordination polymers based on carboxyphenyl-terpyridine ligands.

Hydrothermal synthesis has afforded five divalent zinc coordination polymers containing 4-(4-carboxyphenyl)-2,2':6',2''-terpyridine (HL1) or its isomer 4-(4-carboxyphenyl)-2,2':4',4''-terpyridine (HL2), with or without the addition of auxiliary ligands, 1,3,5-benzenetricarboxylic acid (H3btc) and 1,4-benzenedicarboxylic acid (H2bdc). Their structures have been characterized by single crystal X-ray analyses and further characterized by infrared spectra, elemental analyses, powder X-ray diffraction, thermogravimetric analyses and photoluminescent spectra. Across this series, the π···π interactions have a dramatic impact on the self-assembly of these entanglement structures, in either case it can exert an important structure-directing role. In addition, the disposition of pyridine nitrogen atoms in ligands also plays a large role in structure direction in this system. Complex 1 is a 2D + 2D→3D inclined polycatenated coordination polymer based on the resulting array of 2D (6,3) layers constructed by 1D→2D π···π directed self-assembly. Complex 2 is assembled into a 3D framework by means of 1D + 1D→3D mutual interdigitation based on 1D→1D self-assembly driven by π···π stacking interactions. Complex 3 shows a 2D + 2D→3D interdigital network involving 2D + 2D→2D parallel interpenetrated and 2D + 2D→2D interdigital (4,4) layer motifs. Complex 4 displays a 2D + 2D→3D polythreaded framework based on a 2D (4,4) network comprised of alternating rings and rods. Complex 5 is a (3,4)-connected 3D framework with topology (4.8(2).10(3))(4.8(2)). In comparison with covalently connected entanglements, such π···π directing self-assembly of entanglements are far less explored, especially, polycatenane based on 1D chain motifs and polythread based on 2D layer motifs are rarely reported. Furthermore, the luminescent properties of complexes 1-5 at room temperature have also been studied in detail herein.

Unprecedented three-level hierarchical entanglement in a coordination polymer.

An unprecedented three-level hierarchical entangled system was synthesized. The basic helical ribbons of the complex were entangled into 2D layers by self-penetration based on 1D → 2D polycatenation; a pair of layers interpenetrated, and crosslinked to construct the second self-penetrated bilayers which were further polycatenated into the final 3D entangled array.

The unusual thermochromic NIR luminescence of Cu(I) clusters: tuned by Cu-Cu interactions and packing modes.

Two hexanuclear Cu(I) clusters [Cu(I)(3)(4-ptt)(3)](2)·3DMF·3H(2)O (1) and [Cu(I)(4-ptt)](6)·8DMF·7H(2)O (2) (4-Hptt = 5-(pyridin-4-yl)-1H-1,2,4-triazole-3-thiol, DMF = N,N-dimethylformamide), were synthesized and characterized. Compounds 1 and 2 with similar coordination environments are isomers, but their detailed structures are different due to the reaction temperature tuning effect. Both 1 and 2 extend from monomers to 3D supramolecules with the help of hydrogen bonding between the triazole and pyridine from the 4-ptt ligands. The Cu(6)S(6) units of 1 pack in a polydirectional array, while the Cu(6)S(6) units in 2 extend in one direction and link the planes of adjacent ligands to enhance the delocalization of π electrons. Their varied Cu-Cu interactions and individual packing modes cause differences in luminescent and thermostable behaviors. Compound 1 exhibits an unusually long wavelength at about 900 nm and a higher thermal stability; while the emission of 2 splits into two bands (high-energy and low-energy emission bands) as the temperature decreases. Therefore, the emissions of 1 originate from a (3)CC transition, and those of 2 are from a mixture of (3)CC and MLCT.

Self-assembly of discrete M6L8 coordination cages based on a conformationally flexible tripodal phosphoric triamide ligand.

Reactions of a tripodal ligand, N,N',N″-tris(3-pyridinyl)phosphoric triamide (TPPA), and a series of transition-metal ions result in the assembly of five discrete M(6)L(8) coordination cages [M(6)(TPPA)(8)(H(2)O)(12)](ClO(4))(12)·57H(2)O [M = Ni(2+) (1), Co(2+) (2), Zn(2+) (3), Cd(2+) (4)] and [Pd(6)(TPPA)(8)]Cl(12)·22H(2)O (5). X-ray structural analyses reveal that the cages have large internal cavities and flexible windows. The flexible ligand TPPA adopts the syn conformation in cages 1-4, but it transforms to the anti conformation in cage 5. Because of the conformational transformation, the sizes of the windows and the volume of the internal cavity of cage 5 are increased. (1)H NMR and electrospray mass spectrometric studies show that cage 5 maintains its structural integrity in solution. Additionally, compounds 3 and 4 exhibit strong blue fluorescent emissions, which are 1 order of magnitude higher than that of the free ligand.

A non-interpenetrated porous metal-organic framework with high gas-uptake capacity.

A novel microporous polyhedral framework [Zn(6)(btb)(4)(4,4'-bipy)(3)(dmf)(55)(H(2)O)(32)] with high surface area has been designed and synthesized, which shows high multigas-uptake capacity via supercritical carbon dioxide (SCD) activation.

Preparation of tea catechins using polyamide.

An adsorption separation method using Polyamide-6 (PA) as an adsorbent was developed to separate catechins from green tea extract. The adsorption capacity of total catechins for PA was 193.128 mg g⁻¹ with an adsorption selectivity coefficient K(A)(B) of total catechins over caffeine 21.717, which was better than macroporous resin model HPD 600. The Langmuir model and the pseudo-second order mode were primely fitted to describe its equilibrium data and adsorption kinetics, respectively. PA column separation by two-step elution using water and 80% (v/v) aqueous ethanol was established to prepare catechins complex which contained 670.808 mg g⁻¹ total catechins and 1.828 mg g⁻¹ caffeine. It is considered that PA was a promising adsorbent for selective isolation of catechins.

Green tea polyphenols attenuating ultraviolet B-induced damage to human retinal pigment epithelial cells in vitro.

PURPOSE: To examine the protective effect of green tea polyphenols against ultraviolet B (UVB)-induced damage to retinal pigment epithelial (RPE) cells. METHODS: Green tea polyphenols (GTP) was used to treat RPE cells before or after exposure to UVB. Viability of RPE cells was tested by 3,(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-tetrazolium bromide (MTT) assay. Survivin gene expression was examined by real-time PCR analysis. Ultrastructure of RPE cells was examined by transmission electron microscopy. RESULTS: GTP effectively suppressed the decrease in viability of the UVB stressed RPE cells and the UVB suppression of survivin gene expression level. GTP alleviated mitochondria dysfunction and DNA fragmentation induced by UVB. CONCLUSIONS: GTP protected RPE cells from UVB damage through its increase in the survivin gene expression and its attenuation of mitochondria dysfunction and DNA fragmentation. GTP is a potential candidate for further development as a chemoprotective factor for the primary prevention of age-related eye diseases such as age-related macular degeneration.

A luminescent homochiral 3D Cd(II) framework with a threefold interpenetrating uniform net 8(6).

A luminescent homochiral 3D metal-organic framework, [Cd(dtba)(bpp)](3n) () (H(2)dtba = 2,2'-dithiobisbenzoic acid, bpp = 1,3-bis(4-pyridyl)propane), with an unprecedented threefold interpenetrating uniform network (8(6)), constructed from [Cd(dtba)](n) single helices and [Cd(bpp)](n) double-stranded helices, has been synthesized via hydrothermal reaction.

Cobalt-lanthanide coordination polymers constructed with metalloligands: a ferromagnetic coupled quasi-1D Dy3+ chain showing slow relaxation.

Four types of cobalt-lanthanide heterometallic compounds based on metalloligand Co(2,5-pydc)(3) (3-) (2,5-H(2)pydc=pyridine-2,5-dicarboxylate acid), [Ln(2)Co(2)(2,5-pydc)(6)(H(2)O)(4)](n) 2n H(2)O (1) (Ln=Tb, Dy for 1 a, 1 b respectively), [Tb(2)Co(2)(2,5-pydc)(6)(H(2)O)(4)](n)3n H(2)O (2), [Tb(2)Co(2)(2,5-pydc)(6)(H(2)O)(9)](n)4n H(2)O (3), and [LaCo(2,5-pydc)(3)(H(2)O)(2)](n)2n H(2)O (4) have been synthesized. Compound 1 has a layer structure with well-isolated carboxylate-bridged Ln(3+) chains, compound 2 is a three-dimensional (3D) porous network with Tb(3+) chains that are also well isolated and carboxylate bridged, 3 is a layer structure based on dinuclear units, and 4 is a 3D network with boron nitride (BN) topology. DC magnetic studies reveal ferromagnetic coupling in all the carboxylate-bridged Ln(3+) chains in 1 a, 1 b, and 2. Compared to the silence of the out-of-phase ac susceptibility of 2, above 1.9 K the magnetic relaxation behavior of both 1 a and 1 b is slow like that of a single-chain magnet.

A 3D porous cobalt-organic framework exhibiting spin-canted antiferromagnetism and field-induced spin-flop transition.

Two 3D cobalt-organic frameworks formulated as [Co3(2,4-pydc)2(micro3-OH)2]n.5nH2O (1) and [Co3(2,4-pydc)2(micro3-OH)2(H2O)]n.7nH2O (2) (2,4-pydc=pyridine-2,4-dicarboxylate) have been hydrothermally synthesized and characterized. Both compounds 1 and 2 exhibit the 3D porous frameworks with hydroxyl-bridged metal Delta-chains. However, in comparison with only two crystallographically independent CoII ions in a unit of 2, three crystallographically independent CoII ions are found in an asymmetric unit of 1, where their Delta-chains are constructed by two types of vertexes sharing quadrangles formed via edge-sharing triangles. Magnetic studies show that 1 exhibits spin-canted antiferomagnetism and a field-induced spin-flop transition while 2 behaves as a normal antiferromagnet. The magnetic properties are largely retained by the porous frameworks of dehydrated 1 and 2 compounds. Gas adsorption measurements indicate that both the dehydrated compounds absorb H2 into their pores.