Reversible Switching between Highly Porous and Nonporous Phases of an Interpenetrated Diamondoid Coordination Network That Exhibits Gate‐Opening at Methane Storage Pressures

Herein, we report that a new flexible coordination network, NiL₂ (L=4‐(4‐pyridyl)‐biphenyl‐4‐carboxylic acid), with diamondoid topology switches between non‐porous (closed) and several porous (open) phases at specific CO₂ and CH₄ pressures. These phases are manifested by multi‐step low‐pressure isotherms for CO₂ or a single‐step high‐pressure isotherm for CH₄. The potential methane working capacity of NiL₂ approaches that of compressed natural gas but at much lower pressures. The guest‐induced phase transitions of NiL₂ were studied by single‐crystal XRD, in situ variable pressure powder XRD, synchrotron powder XRD, pressure‐gradient differential scanning calorimetry (P‐DSC), and molecular modeling. The detailed structural information provides insight into the extreme flexibility of NiL₂ . Specifically, the extended linker ligand, L , undergoes ligand contortion and interactions between interpenetrated networks or sorbate–sorbent interactions enable the observed switching.     

Adaptive Chemical Networks under Non‐Equilibrium Conditions: The Evaporating Droplet

Non‐volatile solutes in an evaporating drop experience an out‐of‐equilibrium state due to non‐linear concentration effects and complex flow patterns. Here, we demonstrate a small molecule chemical reaction network that undergoes a rapid adaptation response to the out‐of‐equilibrium conditions inside the droplet leading to control over the molecular constitution and spatial arrangement of the deposition pattern. Adaptation results in a pronounced coffee stain effect and coupling to chemical concentration gradients within the drop is demonstrated. Amplification and suppression of network species are readily identifiable with confocal fluorescence microscopy. We anticipate that these observations will contribute to the design and exploration of out‐of‐equilibrium chemical systems, as well as be useful towards the development of point‐of‐care medical diagnostics and controlled deposition of small molecules through inkjet printing.     

Absolute binding free energies for octa-acids and guests in SAMPL5

As part of the SAMPL5 blind prediction challenge, we calculate the absolute binding free energies of six guest molecules to an octa-acid (OAH) and to a methylated octa-acid (OAMe). We use the double decoupling method via thermodynamic integration (TI) or Hamiltonian replica exchange in connection with the Bennett acceptance ratio (HREM-BAR). We produce the binding poses either through manual docking or by using GalaxyDock-HG, a docking software developed specifically for this study. The root mean square deviations for our most accurate predictions are 1.4 kcal mol^?1 for OAH with TI and 1.9 kcal mol^?1 for OAMe with HREM-BAR. Our best results for OAMe were obtained for systems with ionic concentrations corresponding to the ionic strength of the experimental solution. The most problematic system contains a halogenated guest. Our attempt to model the σ-hole of the bromine using a constrained off-site point charge, does not improve results. We use results from molecular dynamics simulations to argue that the distinct binding affinities of this guest to OAH and OAMe are due to a difference in the flexibility of the host. We believe that the results of this extensive analysis of host-guest complexes will help improve the protocol used in predicting binding affinities for larger systems, such as protein-substrate compounds.     

Direct Air Capture of CO2 by Physisorbent Materials

Sequestration of CO₂, either from gas mixtures or directly from air (direct air capture, DAC), could mitigate carbon emissions. Here five materials are investigated for their ability to adsorb CO₂ directly from air and other gas mixtures. The sorbents studied are benchmark materials that encompass four types of porous material, one chemisorbent, TEPA‐SBA‐15 (amine‐modified mesoporous silica) and four physisorbents: Zeolite 13X (inorganic); HKUST‐1 and Mg‐MOF‐74/Mg‐dobdc (metal–organic frameworks, MOFs); SIFSIX‐3‐Ni , (hybrid ultramicroporous material). Temperature‐programmed desorption (TPD) experiments afforded information about the contents of each sorbent under equilibrium conditions and their ease of recycling. Accelerated stability tests addressed projected shelf‐life of the five sorbents. The four physisorbents were found to be capable of carbon capture from CO₂‐rich gas mixtures, but competition and reaction with atmospheric moisture significantly reduced their DAC performance.     

Banach空间中一类四阶奇异边值问题的解的存在性

利用上下解方法研究了Banach空间中一类四阶奇异两点边值问题的解的存在性.     

Determination of Internal Energy Distributions of Laser Electrospray Mass Spectrometry using Thermometer Ions and Other Biomolecules

The internal energy distributions for dried and liquid samples that were vaporized with femtosecond duration laser pulses centered at 800 nm and postionized by electrospray ionization-mass spectrometry (LEMS) were measured and compared with conventional electrospray ionization mass spectrometry (ESI-MS). The internal energies of the mass spectral techniques were determined by plotting the ratio of the intact parent molecular features to all integrated ion intensities of the fragments as a function of collisional energy using benzylpyridinium salts and peptides. Measurements of dried p-substituted benzylpyridinium salts using LEMS resulted in a greater extent of fragmentation in addition to the benzyl cation. The mean relative internal energies, int> were determined to be 1.62?±?0.06, 2.0?±?0.5, and 1.6?±?0.3 eV for ESI-MS, dried LEMS, and liquid LEMS studies, respectively. Two-photon resonances with the laser pulses likely caused lower survival yields in LEMS analyses of dried samples but not liquid samples. In studies with larger biomolecules, LEMS analyses of dried samples from glass showed a decrease in survival yield compared with conventional ESI-MS for leucine enkephalin and bradykinin of ~15% and 11%, respectively. The survival yields for liquid LEMS analyses were comparable to or better than ESI-MS for benzylpyridinium salts and large biomolecules. Figure

?