Tetraphenylethene-Embedded Pillar[5]arene and [15]Paracyclophane: Distorted Cavities and Host-Guest Binding Properties.

Two aggregation-induced emission (AIE) macrocycles (DMP[5]-TPE and PCP[5]-TPE) were prepared by embedding Tetraphenylethene (TPE) unit into the skeletons of Dimethoxypillar[5]arene (DMP[5]) and [15]Paracyclophane ([15]PCP) at meso position, respectively. In crystal, the PCP[5]-TPE showed a distorted cavity, and the incubation of hexane inside the DMP[5]-TPE cavity caused a distinct change in the molecular conformation compared to PCP[5]-TPE. There was no complexation between PCP[5]-TPE and 1,4-dicyanobutane (DCB). UV absorption experiments showed the distorted cavity of DMP[5]-TPE hindered association with DCB.

Antiviral Activity and Safety of Darunavir/Cobicistat for the Treatment of COVID-19.

BACKGROUND: We aimed to evaluate the antiviral activity and safety of darunavir/cobicistat (DRV/c) in treating COVID-19 patients. METHODS: In this single-center, randomized, and open-label trial, mild patients with polymerase chain reaction (PCR)-confirmed COVID-19 were enrolled in Shanghai, China. Participants were randomized to receive DRV/c for 5 days on the top of interferon alpha 2b inhaling or interferon alpha 2b inhaling alone. The primary end point was the virological clearance rate of oropharyngeal swabs at day 7 after randomization in the intention-to-treat population (clinicaltrials.gov: NCT04252274). RESULTS: From January 30, 2020, to February 6, 2020, a total of 30 patients were enrolled, of whom 18 (60%) were male, aged 47.2 ±â€…2.8 years; 63.3% (19/30) of the participants had fever, and 46.7% (14/30) had cough at enrollment. The participants were randomized (range) at 4 (2-5) days after onset of symptoms. The proportion of negative PCR results at day 7 was 46.7% (7/15) and 60.0% (9/15) in the DRV/c and control groups (P = .72), respectively. The viral clearance rate at day 3 was 20% (3/15) in both study groups, while the number increased to 26.7% (4/15) in the DRV/c group and remained 20% (3/15) in the control group at day 5. Fourteen days after randomization, 1 participant in the DRV/c group progressed to critical illness and discontinued DRV/c, while all the patients in the control group were stable (P = 1.0). The frequencies of adverse events in the 2 groups were comparable. CONCLUSIONS: Five days of DRV/c did not increase the proportion of negative conversion vs standard of care alone, although it was well tolerated.

Supramolecular strategy for smart windows.

Smart windows are a promising solution to improve energy-saving efficiency and indoor comfort due to their potential functionalities including solar modulation, coloration, self-cleaning, self-power, and moisture scavenging. Recently, smart windows constructed by a supramolecular strategy have attracted increasing attention due to the inherent dynamic, reversible and adaptive properties of noncovalent interactions, which can endow the fabricated smart windows with desired fascinating functionalities. In this review, emerging supramolecular strategy-based materials are outlined and their applications for fabricating smart windows are summarized. Mechanisms and properties of the functional supramolecular materials are demonstrated, especially their solar modulation ability and color change effect. Challenges and opportunities for the supramolecular strategy-based materials are also discussed for future innovation in the development of ideal smart windows.

Warm/cool-tone switchable thermochromic material for smart windows by orthogonally integrating properties of pillar[6]arene and ferrocene.

Functional materials play a vital role in the fabrication of smart windows, which can provide a more comfortable indoor environment for humans to enjoy a better lifestyle. Traditional materials for smart windows tend to possess only a single functionality with the purpose of regulating the input of solar energy. However, different color tones also have great influences on human emotions. Herein, a strategy for orthogonal integration of different properties is proposed, namely the thermo-responsiveness of ethylene glycol-modified pillar[6]arene (EGP6) and the redox-induced reversible color switching of ferrocene/ferrocenium groups are orthogonally integrated into one system. This gives rise to a material with cooperative and non-interfering dual functions, featuring both thermochromism and warm/cool tone-switchability. Consequently, the obtained bifunctional material for fabricating smart windows can not only regulate the input of solar energy but also can provide a more comfortable color tone to improve the feelings and emotions of people in indoor environments.

Multistimuli-responsive supramolecular vesicles based on water-soluble pillar[6]arene and SAINT complexation for controllable drug release.

Supramolecular binary vesicles based on the host-guest complexation of water-soluble pillar[6]arene (WP6) and SAINT molecule have been successfully constructed, which showed pH-, Ca(2+)-, and thermal-responsiveness. These supramolecular vesicles can efficiently encapsulate model substrate calcein, which then can be efficiently released either by adjusting the solution pH to acidic condition due to the complete disruption of vesicular structure, or particularly, by adding a certain amount of Ca(2+) due to the Ca(2+)-induced vesicle fusion and accompanied by the structure disruption. More importantly, drug loading and releasing experiments demonstrate that an anticancer drug, DOX, can be successfully encapsulated by the supramolecular vesicles, and the resulting DOX-loaded vesicles exhibit efficient release of the encapsulated DOX with the pH adjustment or the introduction of Ca(2+). Cytotoxicity experiments suggest that the resulting DOX-loaded supramolecular vesicles exhibit comparable therapeutic effect for cancer cells as free DOX and the remarkably reduced damage for normal cells as well. The present multistimuli-responsive supramolecular vesicles have great potential applications in the field of controlled drug delivery. In addition, giant supramolecular vesicles (~3 µm) with large internal volume and good stability can be achieved by increasing the temperature of WP6 ⊃ SAINT vesicular solution, and they might have potential applications for bioimaging.

Two lanthanum(III) complexes containing η2-pyrazolate and η2-1,2,4-triazolate ligands: intramolecular C-H...N/O interactions and coordination geometries.

The lanthanum(III) complexes tris(3,5-diphenylpyrazolato-κ(2)N,N')tris(tetrahydrofuran-κO)lanthanum(III) tetrahydrofuran monosolvate, [La(C(15)H(11)N(2))(3)(C(4)H(8)O)(3)]·C(4)H(8)O, (I), and tris(3,5-diphenyl-1,2,4-triazolato-κ(2)N(1),N(2))tris(tetrahydrofuran-κO)lanthanum(III), [La(C(14)H(10)N(3))(3)(C(4)H(8)O)(3)], (II), both contain La(III) atoms coordinated by three heterocyclic ligands and three tetrahydrofuran ligands, but their coordination geometries differ. Complex (I) has a mer-distorted octahedral geometry, while complex (II) has a fac-distorted configuration. The difference in the coordination geometries and the existence of asymmetric La-N bonding in the two complexes is associated with intramolecular C-H...N/O interactions between the ligands.

Bis{1-[(benzo-yloxy)meth-yl]-1H-1,2,3-benzotriazole-κN(3)}(nitrato-κ(2)O,O')-silver(I).

In the crystal structure of the title coordination compound, [Ag(NO(3))(C(14)H(11)N(3)O(2))(2)], the Ag(I) atom is four-coordinated in a distorted tetra-hedral geometry by two O atoms from one nitrate group and two N atoms from two different 1-[(benzo-yloxy)meth-yl]-1H-1,2,3-triazole ligands. In the complex, the two coordinated benzotriazole rings rings are nearly perpendicular, the dihedral angle between their planes being 87.08 (6)°.

(1H-1,2,3-Benzotriazol-1-yl)methyl 2,2-dimethyl-propano-ate.

In the title compound, C(12)H(15)N(3)O(2), the dihedral angle between the mean planes of the benzene and triazole rings is 0.331 (53) °. The side chain of the pivalate unit forms a dihedral angle of 69.04 (12)° with the benzotriazole unit. The ester group and two methyl groups of the pivalate unit are disordered with an occupancy ratio of 0.731 (3):0.269 (3). In the crystal, weak π-π stacking inter-actions are observed between inversion-related benzene rings [centroid-centroid distance = 3.9040 (1) Å].

Synthesis, characterization and metal ion-sensing properties of two Schiff base derivatives.

Two new Schiff base derivatives {2,2'-diphenyl-N,N'-bis(2-pyridylmethylene)biphenyl-4,4'-diamine} (1) and {2,2'-diphenyl-N,N'-bis(salicylidene)biphenyl-4,4'-diamine} (2) were synthesized and characterized by means of elemental analysis, (1)H NMR, FT-IR, and standard spectroscopy techniques. The molecular structure of 2 has been determined by X-ray single crystal analysis. The analyses of fluorescence properties of the compounds revealed that 1 and 2 are both poorly fluorescent and display sensitive fluorescence responses to a panel of 24 monovalent, divalent, and trivalent metal ions in CH(3)CN-DMSO (9:1, v/v). Results with imine 1 showed that Fe(3+), Cu(2+), Zn(2+), Cd(2+), Mn(2+), Zr(4+), Hg(2+), Cr(2+), Pb(2+), Sn(2+), Bi(2+), Al(3+), Ce(3+), La(3+), Sm(3+), Gd(3+), Nd(3+), Eu(3+) and Dy(3+) yields red shifts in emission and increases in intensity. And the greatest spectral changes for imine 2 include enhancements in emission intensity coupled with red shifts (Zr(4+), Sn(2+), Al(3+) and Zn(2+)) and strong quenching (Fe(3+)). The fluorescence enhancement mechanism of 1 and 2 for metal ions is based on: (i) CN isomerization; (ii) chelation-enhanced fluorescence (CHEF) effect; and (iii) excited-state intra/intermolecular proton transfer (ESPT).

Ligand-free copper-catalyzed regioselective C-2 arylation of imidazo[2,1-b]thiazoles.

An effective, regioselective C-2 arylation of imidazo[2,1-b]thiazoles catalyzed by Cu(I) has been developed. This arylation proceeded smoothly without promotion of the ligands, and various functional (22 samples) groups were well tolerated. Preliminary mechanistic studies of this arylation are also reported.

Organophosphine/phosphite stabilized disilver(I) methanedisulphonates: synthesis, solid state structures and their potential use as MOCVD precursors.

New disilver(I) methanedisulphonate complexes [CH(2)(SO(3))(2)Ag(2)·L(n)] (L = PPh(3); n=2, 2a; n=3, 2b; n=4, 2c; n=5, 2d; n=6, 2e; L=P(OEt)(3); n=2, 2f; n=4, 2g; n=6, 2h) were prepared by the reaction of [CH(2)(SO(3))(2)Ag(2)], which could be synthesized from methanedisulphonic acid and Ag(2)CO(3) in water, with triphenylphosphine or triethylphosphite in dichloromethane under a nitrogen atmosphere. The solid state structures of three complexes 2c, 2d and 2f were determined by single X-ray structure analysis. Hot-wall metal organic chemical vapor deposition (MOCVD) experiments were carried out at 395 °C, 420 °C and 450 °C using 2g as precursor for the deposition of silver films, respectively. The silver film with high purity obtained at 420 °C is dense and homogeneous, which is composed of many well isolated, granular particulates spreading all over the substrate surface.

Bis[µ-N,N'-bis(quinolin-8-yl)pyridine-2,6-dicarboxamido]dizinc(II) dichloromethane disolvate.

The title compound, [Zn(2)(C(25)H(15)N(5)O(2))(2)]·2CH(2)Cl(2), is a dinuclear double-helical complex which lies on a crystallographic twofold axis. In the complex, both ligands are partitioned into two tridentate domains which allow each ligand to bridge both metal centres. Each Zn(II) atom is six-coordinated in a distorted octahedral environment formed by two amide N atoms, two quinoline N atoms and two pyridine N atoms from two different ligand molecules, with the central pyridine ring, unusually, bridging two Zn(II) atoms. The deprotonated ligand is not planar, the amide side chains being considerably twisted out from the plane of the central pyridine ring.

Phosphite copper(I) trifluoroacetates [((RO)3P)mCuO2CCF3] (m = 1, 2, 3): synthesis, solid state structures and their potential use as CVD precursors.

Metal-organics [((RO)(3)P)(m)CuO(2)CCF(3)] (R = CH(3): 11a, m = 1; 11b, m = 2; 11c, m = 3. R = CH(2)CH(3): 12a, m = 1; 12b, m = 2; 12c, m = 3. R = CH(2)CF(3): 13a, m = 1; 13b, m = 2; 13c, m = 3) are either accessible by the reaction of [((RO)(3)P)(m)CuCl] (R = CH(3): 5a, m = 1; 5b, m = 2; 5c, m = 3. R = CH(2)CH(3): 6a, m = 1; 6b, m = 2; 6c, m = 3) with [KO(2)CCF(3)] (7), or treatment of [Cu(2)O] (8) with HO(2)CCF(3) (9) and P(OR)(3) (2, R = CH(3); 3, R = CH(2)CH(3); 4, R = CH(2)CF(3)). (31)P{(1)H} NMR spectra [((CH(3)O)(3)P)(m)CuO(2)CCF(3)] (m = 1, 1.5, 2, 2.5, 3, 3.5, and 4) have been studied at 25 and -80 °C showing phosphite ligand exchange in solution. The molecular structures of 11a and 13a-13c in the solid state are reported. Complexes 11a and 13a are tetramers featuring µ-η(2)(1κO:2κO')- and µ(3)-η(2)(1κO:2κO':3κO')-(11a) or µ(3)-η(2)(1κO:2κO':3κO')-bonded O(2)CCF(3) ligands (13a) with the Cu(I) ions being part of CuPO(2) and CuPO(3) units (11a), while in 13a solely a CuPO(3) moiety is present. Skeletal isomerism of 11a vs. 13a is discussed. Compound 13b is dimeric ({CuP(2)O(2)}(2)) with pseudo-tetrahedral Cu environments and µ-η(2)(1κO:2κO')O(2)CCF(3) functionalities. In monomeric 13c the O(2)CCF(3) ligand is η(1)(κO)-bonded to a tetra-coordinated Cu(i) ion. The thermal solid state properties of 11, 12 and 13 were studied by Thermo Gravimetry (TG). These complexes decompose by phosphite elimination, decarboxylation and dealkylation. Hot-wall Chemical Vapour Deposition (CVD) experiments were carried out at 380 °C using 11c as precursor for the deposition of copper onto pieces of TiN-coated oxidized silicon substrates. Copper layers of high purity were obtained with grain sizes between 200-1200 nm.

Unprecedented NaI-CuII-LnIII heterometallic coordination polymers based on 3,5-pyrazoledicarboxylate with both infinite cationic and anionic chains.

The self-assembly of 3,5-pyrazoledicarboxylic acid (H3pdc) and metal salts under hydrothermal conditions leads to the formation of a series of novel NaI-CuII-LnIII heterometallic coordination polymers, [[Na(H2O)4]2[Cu(pdc)2Ln(H2O)5]2 x 3H2O]n [Ln = La (1); Sm (2); Pr (3); Nd (4) and pdc3- = 3,5-pyrazoledicarboxylate]. X-Ray structure analyses show that these complexes all exhibit pairs of infinite, unexpected, cationic and anionic chains. It is the first successful attempt to construct unprecedented NaI-CuII-LnIII heterometallic coordination polymers with both infinite cationic and anionic chains. These four complexes show homologous thermal stabilities. The different magnetic properties of are also been reported in this paper.

A novel three-dimensional heterometalliccoordination polymer:poly[[hexaaquabis[mu3-3,5-dicarboxylatopyrazolato-kappa5O3,N2:N1,O5:O50]-(mu2-oxalato-kappa4O1,O2:O10,O20)-copper(II)dierbium(III)] trihydrate].

The title novel heterometallic 3d-4f coordination polymer, {[CuEr(2)(C(5)HN(2)O(4))(2)(C(2)O(4))(H(2)O)(6)].3H(2)O}(n), has a three-dimensional metal-organic framework composed of two types of metal atoms (one Cu(II) and two Er(III)) and two types of bridging anionic ligands [3,5-dicarboxylatopyrazolate(3-) (ptc(3-)) and oxalate]. The Cu(II) atom is four-coordinated in a square geometry. The Er(III) atoms are both eight-coordinated, but the geometries at the two atoms appear different, viz. triangular dodecahedral and bicapped trigonal prismatic. One of the oxalate anions is located on a twofold axis and the other lies about an inversion centre. Both oxalate anions act as bis-bidentate ligands bridging the latter type of Er atoms in parallel zigzag chains. The pdc(3-) anions act as quinquedentate ligands not only chelating the Cu(II) and the triangular dodecahedral Er(III) centres in a bis-bidentate bridging mode, but also connecting to Er(III) centres of both types in a monodentate bridging mode. Thus, a three-dimensional metal-organic framework is generated, and hydrogen bonds link the metal-organic framework with the uncoordinated water molecules. This study describes the first example of a three-dimensional 3d-4f coordination polymer based on pyrazole-3,5-dicarboxylate and oxalate, and therefore demonstrates further the usefulness of pyrazoledicarboxylate as a versatile multidentate ligand for constructing heterometallic 3d-4f coordination polymers with interesting architectures.

Poly[[tetra-aqua-(µ(6)-2,2'-diiodo-biphenyl-4,4',5,5'-tetra-carboxyl-ato)dizinc(II)] dihydrate].

In the title compound, {[Zn(2)(C(16)H(4)I(2)O(8))(H(2)O)(4)]·2H(2)O}(n), two crystallographically independent Zn(II) atoms are each located on a twofold rotation axis. Both Zn(II) atoms are in distorted octa-hedral coordination geometries: one is coordinated by six O atoms from four carboxyl-ate groups, while the other is coordinated by two carboxyl-ate groups and four water mol-ecules. The tetra-carboxyl-ate ligand mol-ecules connect the Zn(II) atoms, completing a three-dimensional metal-organic framework. O-H⋯O hydrogen bonds link the metal-organic framework with the uncoord-inated water mol-ecules.