Pulsating Polymer Micelles via ATP-Fueled Dissipative Self-Assembly

Energy dissipation underlies dynamic behaviors of the life system. This principle of biology is explicit, but its in vitro mimic is very challenging. Here we use an energy-dissipative self-assembly pathway to create a life-like polymer micellar system that can do periodic and self-adaptive pulsating motion fueled by cell energy currency, adenosine triphosphate (ATP). Such a micelle expansion–contraction behavior relies on transient supramolecular interactions between the micelle and ATP fuel. The micelles capturing ATPs will deviate away from the thermodynamic equilibrium state, driving a continuous micellar expansion that temporarily breaks the amphiphilic balance, until a competing ATP hydrolysis consumes energy to result in an opposing micellar contraction. As long as ATP energy is supplied to keep the system in out-of-equilibrium, this reciprocating process can be sustained, and the ATP level can orchestrate the rhythm and amplitude of nanoparticulate pulsation. The man-made assemblies provide a model for imitating biologically time-dependent self-assembly and periodic nanocarriers for programmed drug delivery

Field-Induced Relaxation of Magnetization in a Three-Dimensional LnMOF with the Second Bridging Ligand Squarate

A three-dimensional (3D) dysprosium­(III) metal-organic framework with nicotinate <i>N</i>-oxide (NNO^–) and squarate (C₄O₄^2–) mixed bridging ligands, [Dy­(NNO)­(C₄O₄)­(H₂O)]<i>_n</i> (<b>1</b>), has been hydrothermally synthesized. The dysprosium­(III) ions are linked to each other by the squarate anions to form a unique dysprosium­(III) squarate double-layered network; the NNO^– anions then bridge such layers to complete the 3D framework. Complex <b>1</b> exhibits a two-step relaxation of magnetization under a dc field of 1000 Oe, with effective energy barrier values of 8.5 and 14.3 K, respectively

Supplementary document for Modeling off-axis diffraction with adaptive-sampling angular spectrum method - 6442441.pdf

Supplement material with additional results, proof, and derivation

Rigorous and efficient diffraction modeling between arbitrary planes by angular spectrum rearrangement

In computational optics, numerical modeling of diffraction between arbitrary planes offers unparalleled flexibility. However, existing methods suffer from the trade-off between computational accuracy and efficiency. To resolve this dilemma, we present a novel approach that rigorously and efficiently models wave propagation between two arbitrary planes. This is achieved by rearranging the angular spectrum of the source field, coupled with linear algebraic computations. Notably, our method achieves comparable computational efficiency to the control method for both scalar and vectorial diffraction modeling, while eliminating nearly all numerical errors. Furthermore, we selectively merge the angular spectrum to further enhance the efficiency at the expense of precision in a controlled manner. Thereafter, the time consumption is reduced to at most 3% of that before merging

Supplementary document for Investigating deep optics model representation in affecting resolved all-in-focus image quality and depth estimation fidelity - 6046849.pdf

revised supplemental materia

Syntheses, Crystal Structures, and Magnetic Properties of Two <i>p</i>-<i>tert</i>-Butylsulfonylcalix[4]arene Supported Cluster Complexes with a Totally Disordered Ln₄(OH)₄ Cubane Core

Two new sandwich calix[4]­arene-supported cluster complexes, [Ln₄(OH)₄­(TBSOC)₂­(H₂O)₄­(CH₃OH)₄]­·4H₂O (H₄TBSOC = <i>p</i>-<i>tert</i>-butylsulfonylcalix­[4]­arene; Ln = Dy, <b>1</b>; Ln = Ho, <b>2</b>), have been prepared and characterized. An X-ray crystallographic study reveals that both complexes contain a holistically disordered [Ln₄(OH)₄]⁸⁺ cubane cluster core, which is sandwiched between two antiparallel calixarene macrocycles. Magnetic investigations indicate that complex <b>1</b> displays slow magnetization relaxation typical for single-molecule magnets in the absence of a static applied dc field, with the Δ<i><i>E</i>/k</i>_B parameter of 22.9 K, the largest value for the calixarene-supported pure 4f single-molecule magnets so far, whereas complex <b>2</b> does not show any relaxation of the magnetization above 2 K

Arraying Octahedral {Cr₂Dy₄} Units into 3D Single-Molecule-Magnet-Like Inorganic Compounds with Sulfate Bridges

Two novel 3D pure inorganic compounds based on [Cr₂Dy₄(μ₄-O)₂(μ₃-OH)₄]¹⁰⁺ cluster units and sulfate anions are presented. Both complexes exhibit single-molecule-magnet (SMM)-like behavior. Permutation of the magnetic moment direction among SMM-like cluster units has a significant effect on the performance of molecular nanomagnets, and directional consistency shows obvious advantages

Syntheses, Crystal Structures, and Magnetic Properties of Two <i>p</i>-<i>tert</i>-Butylsulfonylcalix[4]arene Supported Cluster Complexes with a Totally Disordered Ln₄(OH)₄ Cubane Core

Two new sandwich calix[4]­arene-supported cluster complexes, [Ln₄(OH)₄­(TBSOC)₂­(H₂O)₄­(CH₃OH)₄]­·4H₂O (H₄TBSOC = <i>p</i>-<i>tert</i>-butylsulfonylcalix­[4]­arene; Ln = Dy, <b>1</b>; Ln = Ho, <b>2</b>), have been prepared and characterized. An X-ray crystallographic study reveals that both complexes contain a holistically disordered [Ln₄(OH)₄]⁸⁺ cubane cluster core, which is sandwiched between two antiparallel calixarene macrocycles. Magnetic investigations indicate that complex <b>1</b> displays slow magnetization relaxation typical for single-molecule magnets in the absence of a static applied dc field, with the Δ<i><i>E</i>/k</i>_B parameter of 22.9 K, the largest value for the calixarene-supported pure 4f single-molecule magnets so far, whereas complex <b>2</b> does not show any relaxation of the magnetization above 2 K

Soluble Silver Acetylide for the Construction and Structural Conversion of All-Alkynyl-Stabilized High-Nuclearity Homoleptic Silver Clusters

Silver acetylide complex [Ag­(ArCC)]_<i>n</i> (Ar = 3,5-di-<i>tert</i>-butylphenyl) with unprecedented high solubility in common organic solvents has been designed and synthesized. The high solubility is due to two bulky <i>tert</i>-butyl substituents on the phenyl ring. This feature is significant to construct and isolate single crystals of all-alkynyl-stabilized silver clusters, which are crucial to investigate the intrinsic binding interaction and coordination modes between Ag­(I) and ethynide ligands. Crystallization of [Ag­(ArCC)]_<i>n</i> under various conditions resulted in three high-nuclearity homoleptic silver acetylide clusters, namely, [Ag₂₁(ArCC)₂₀]­(OH) (<b>1</b>), [Ag₁₆(ArCC)₁₆] (<b>2</b>), and [Ag₁₅(ArCC)₁₅] (<b>3</b>). Complex <b>1</b> has a [Ag₂₁] cluster protected by twenty 3,5-di-<i>tert</i>-butyl-phenylethynide ligands. Complexes <b>2</b> and <b>3</b> have neutral [Ag₁₆] and [Ag₁₅] clusters, respectively. In addition to these homoleptic silver clusters, two new silver acetylides [Ag₂₀(ArCC)₁₆(CH₃COO)₄] (<b>4</b>) and [Ag₂₂(ArCC)₁₆(NO₃)₄(CH₃CH₂OH)₄]­(OH)₂ (<b>5</b>) were synthesized. The acetate and nitrate anions in these structures are more like counterions instead of acting as critical building blocks or templates for cluster assembly. These results illustrated the significance of 3,5-di-<i>tert</i>-butyl-phenylethynide ligands in the construction and stabilization of high-nuclearity silver clusters. Analysis of structures of <b>1</b>–<b>5</b> revealed several novel coordination modes between Ag­(I) and ethynide ligands, which contributed considerably to our knowledge of Ag­(I)–ethynide binding interactions

Chloroyttrium 2‑(1-(Arylimino)alkyl)quinolin-8-olate Complexes: Synthesis, Characterization, and Catalysis of the Ring-Opening Polymerization of ε‑Caprolactone

Stoichiometric reactions of YCl₃(THF)₃ with potassium 2-((arylimino)­methyl)­quinolin-8-olates or 2-(1-(arylimino)­ethyl)­quinolin-8-olates in THF solution gave the mononuclear LYCl₂(DMSO)₂ complexes <b>1</b>–<b>5</b> in the presence of DMSO and a representative dinuclear complex <b>6</b> in the absence of DMSO. All yttrium complexes were fully characterized by NMR measurements and elemental analysis, and the crystal structures of complexes <b>1</b> and <b>4</b>–<b>6</b> were determined by single-crystal X-ray diffraction. The structures indicate coordination number seven around the yttrium center and pentagonal bipyramidal geometries. The complexes all feature diapical YCl₂ moieties and one tridentate organic ligand in the equatorial plane. Upon reaction of the yttrium precatalysts <b>1</b>–<b>6</b> with LiCH₂Si­(CH₃)₃ alone or with LiCH₂Si­(CH₃)₃ together with BnOH, the ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) occurred with high efficiency. Depending on conditions, the ROP of ε-CL produced polycaprolactone with narrow molecular distribution and in a living manner. Theoretical studies of the chlorine/CH₂SiMe₃ and Me₃SiCH₂/BnO ligand exchange reactions suggest that the replacement of the apical ligands can proceed without significantly affecting the equatorial ligands. These results suggest that one of the apical Y–CH₂SiMe₃ bonds within the LY­(CH₂SiMe₃)₂ intermediate catalyzes the polymerization in the BnOH-free process. Most polymers generated by BnOH-assisted catalysis possess <i>M</i>_n values that are similar to <i>M</i>_n,cal values based on Y–OBn, suggesting that one apical Y–OBn bond of the diapical LY­(OBn)­(CH₂SiMe₃) intermediate catalyzes most or all of the ring polymerization of ε-CL