Isoreticular Curves: A Theory of Capillary Condensation To Model Water Sorption within Microporous Sorbents.

Metal-organic frameworks have gained traction as leading materials for water sorption applications due to precise chemical tunability of their well-ordered pores. These applications include atmospheric water capture, heat pumps, desiccation, desalination, humidity control, and thermal batteries. However, the relationships between the framework pore structure and the measurable water sorption properties, namely critical relative humidity for condensation, maximal capacity, and pore size or temperature for the onset of hysteresis, have not been clearly delineated.

Superior Charge Transport in Ni-Diamine Conductive MOFs.

Two-dimensional conductive metal-organic frameworks (2D cMOFs) are an emerging class of crystalline van der Waals layered materials with tunable porosity and high electrical conductivity. They have been used in a variety of applications, such as energy storage and conversion, chemiresistive sensing, and quantum information. Although designing new conductive 2D cMOFs and studying their composition/structure-property relationships have attracted significant attention, there are still very few examples of 2D cMOFs that exhibit room-temperature electrical conductivity above 1 S cm, the value exhibited by activated carbon, a well-known porous and conductive material that serves in myriad applications.

Humidity-Mediated Dual Ionic-Electronic Conductivity Enables High Sensitivity in MOF Chemiresistors.

In the presence of water, the electrically conductive metal-organic framework (MOF) CuHHTT (HHHTT = 2,3,7,8,12,13-hexahydroxy-4b1,5,10,15-tetraazanaphtho[1,2,3-gh]tetraphene) provides a conduit for proton transport, thereby becoming a dual ionic-electronic conductor. Owing to its dual conducting nature and its high density of imine and open metal sites, the MOF operates as a particularly sensitive chemiresistor, whose sensing mechanism changes with relative humidity. Thus, the interaction of NH gas with the MOF under low humidity promotes proton transport, which translates to high sensitivity for ammonia detection.

A comprehensive pediatric cardio-oncology program: a single institution approach to cardiovascular care for pediatric patients with cancer and childhood cancer survivors.

Cardiovascular complications related to cancer therapies are broad and variable in onset. These complications are the leading cause of non-cancer related morbidity and mortality in childhood cancer survivors and can also impact ongoing cancer treatment. Despite this understanding, dedicated cardio-oncology programs are lacking in pediatric cardiology.

A Layered Organic Cathode for High-Energy, Fast-Charging, and Long-Lasting Li-Ion Batteries.

Eliminating the use of critical metals in cathode materials can accelerate global adoption of rechargeable lithium-ion batteries. Organic cathode materials, derived entirely from earth-abundant elements, are in principle ideal alternatives but have not yet challenged inorganic cathodes due to poor conductivity, low practical storage capacity, or poor cyclability. Here, we describe a layered organic electrode material whose high electrical conductivity, high storage capacity, and complete insolubility enable reversible intercalation of Li ions, allowing it to compete at the electrode level, in all relevant metrics, with inorganic-based lithium-ion battery cathodes.

LTX-315 triggers anticancer immunity by inducing MyD88-dependent maturation of dendritic cells.

LTX-315 is a synthetic cationic oncolytic peptide with potent anticancer activity but limited toxicity for non-malignant cells. LTX-315 induces both immunogenic tumor cell death and generation of tumor-specific immune responses in multiple experimental tumor models. Given the central role of dendritic cell (DC) maturation in the induction of antigen-specific immunity, we investigated the effect of LTX-315 treatment on the maturation of tumor-infiltrating DCs (TiDCs) and the generation of anti-melanoma immunity.

Gravitationally induced decoherence vs space-time diffusion: testing the quantum nature of gravity.

We consider two interacting systems when one is treated classically while the other system remains quantum. Consistent dynamics of this coupling has been shown to exist, and explored in the context of treating space-time classically. Here, we prove that any such hybrid dynamics necessarily results in decoherence of the quantum system, and a breakdown in predictability in the classical phase space.

A Solid Zn-Ion Conductor from an All-Zinc Metal-Organic Framework Replete with Mobile Zn Cations.

We describe the synthesis and properties of Zn[(ZnCl)(BTT)] (ZnZnBTT, BTT = 1,3,5-benzenetristetrazolate), a heretofore unknown member of a well-known, extensive family of metal-organic frameworks (MOFs) with the general formula M[(MCl)(BTT)], which adopts an anionic, sodalite-like structure. As with previous members in this family, ZnZnBTT presents two crystallographically distinct metal cations: a skeletal Zn site, fixed within ZnCl(tetrazole) secondary building units (SBUs), and a charge-balancing Zn site. Self-assembly of ZnZnBTT from its building blocks has remained elusive; instead, we show that ZnZnBTT is readily accessed by quantitative postsynthetic exchange of all Mn ions in MnMnBTT with zinc.

Tunable Low-Relative Humidity and High-Capacity Water Adsorption in a Bibenzotriazole Metal-Organic Framework.

Materials capable of selectively adsorbing or releasing water can enable valuable applications ranging from efficient humidity and temperature control to the direct atmospheric capture of potable water. Despite recent progress in employing metal-organic frameworks (MOFs) as privileged water sorbents, developing a readily accessible, water-stable MOF platform that can be systematically modified for high water uptake at low relative humidity remains a significant challenge. We herein report the development of a tunable MOF that efficiently captures atmospheric water (up to 0.

Development of a novel modified vaccine (TheraVac) for curative treatment of mouse solid tumors.

Monotherapy with immune checkpoint blockade (ICB) antibodies (anti-CTLA4 and anti-PD1/PDL-1) is only effective for 20% to 30% of patients with certain cancers. Patients with cancers harboring few effector T cells (Teffs) are insensitive to ICB therapy. The lack of tumor-specific Teffs is predominantly caused by the paralysis of tumor-infiltrating dendritic cells (TiDCs) resulting from immunosuppression in the tumor microenvironment.

Ultrafast Water H-Bond Rearrangement in a Metal-Organic Framework Probed by Femtosecond Time-Resolved Infrared Spectroscopy.

We investigated the water H-bond network and its dynamics in NiClBTDD, a prototypical MOF for atmospheric water harvesting, using linear and ultrafast IR spectroscopy. Utilizing isotopic labeling and infrared spectroscopy, we found that water forms an extensive H-bonding network in NiClBTDD. Further investigation with ultrafast spectroscopy revealed that water can reorient in a confined cone up to ∼50° within 1.

Regression and Eradication of Triple-Negative Breast Carcinoma in 4T1 Mouse Model by Combination Immunotherapies.

Triple-negative breast carcinoma (TNBC) is one of the most aggressive types of solid-organ cancers. While immune checkpoint blockade (ICB) therapy has significantly improved outcomes in certain types of solid-organ cancers, patients with immunologically cold TNBC are afforded only a modest gain in survival by the addition of ICB to systemic chemotherapy. Thus, it is urgently needed to develop novel effective therapeutic approaches for TNBC.

A Therapeutic Vaccine in Combination with Cyclic GMP-AMP Cures More Differentiated Melanomas in Mice.

We have identified a combinational immunotherapy termed TheraVac vaccine (TheraVac) that can cure multiple large established mouse tumors, but it failed to cure melanoma in mice. TheraVac consists of an immunostimulating arm containing an agonist (HMGN1 [N1]) for TLR4 and an agonist (R848) for TLR7/8 that synergize to activate tumor-infiltrating dendritic cells (DCs) and promote Th1 immune responses. The second arm uses an immune checkpoint blockade, anti-PDL-1, to diminish tumor-associated immunosuppression.

Conceptual and Practical Aspects of Metal-Organic Frameworks for Solid-Gas Reactions.

The presence of site-isolated and well-defined metal sites has enabled the use of metal-organic frameworks (MOFs) as catalysts that can be rationally modulated. Because MOFs can be addressed and manipulated through molecular synthetic pathways, they are chemically similar to molecular catalysts. They are, nevertheless, solid-state materials and therefore can be thought of as privileged solid molecular catalysts that excel in applications involving gas-phase reactions.

Solid-State Investigation, Storage, and Separation of Pyrophoric PH and P H with α-Mg Formate.

Phosphane, PH -a highly pyrophoric and toxic gas-is frequently contaminated with H and P H , which makes its handling even more dangerous. The inexpensive metal-organic framework (MOF) magnesium formate, α-[Mg(O CH) ], can adsorb up to 10 wt % of PH . The PH -loaded MOF, PH @α-[Mg(O CH) ], is a non-pyrophoric, recoverable material that even allows brief handling in air, thereby minimizing the hazards associated with the handling and transport of phosphane.

TNFR2 antagonistic antibody induces the death of tumor infiltrating CD4Foxp3 regulatory T cells.

Background: TNFR2 expression is a characteristic of highly potent immunosuppressive tumor infiltrating CD4Foxp3 regulatory T cells (Tregs). There is compelling evidence that TNF through TNFR2 preferentially stimulates the activation and expansion of Tregs. We and others, therefore, proposed that targeting TNFR2 may provide a novel strategy in cancer immunotherapy.

Dipole-mediated exciton management strategy enabled by reticular chemistry.

Selectively blocking undesirable exciton transfer pathways is crucial for utilizing exciton conversion processes that involve participation of multiple chromophores. This is particularly challenging for solid-state systems, where the chromophores are fixed in close proximity. For instance, the low efficiency of solid-state triplet-triplet upconversion calls for inhibiting the parasitic singlet back-transfer without blocking the flow of triplet excitons.

Pyrogallate-Based Metal-Organic Framework with a Two-Dimensional Secondary Building Unit.

We report a metal-organic framework (MOF) with a rare two-dimensional (2D) secondary building unit (SBU). The SBU comprises mixed-valent Fe and Fe metal ions bridged by oxygen atoms pertaining to the polytopic ligand 3,3',4,4',5,5'-hexahydroxybiphenyl, which also define the iron-oxide 2D layers. Overall, the anionic framework exhibits rare topology and evidences strong electronic communication between the mixed-valence iron sites.

Thousand-fold increase in O electroreduction rates with conductive MOFs.

Molecular materials must deliver high current densities to be competitive with traditional heterogeneous catalysts. Despite their high density of active sites, it has been unclear why the reported O reduction reaction (ORR) activity of molecularly defined conductive metal-organic frameworks (MOFs) have been very low: ca. -1 mA cm.

Strong magnetic exchange coupling in a radical-bridged trinuclear nickel complex.

Reaction of 2,3,6,7,10,11-hexaaminotriphenylene hexahydrochloride (HATP·6HCl) and (TpNi)Cl (Tp = tris(3,5-diphenyl-1-pyrazolyl)borate) produces the radical-bridged trinickel complex [(TpNi)(HITP)] (HITP˙ = 2,3,6,7,10,11-hexaiminotriphenylene). Magnetic measurements and broken-symmetry density functional theory calculations reveal strong exchange coupling persisting at room temperature between HITP˙ and two of the three Ni centers, a rare example of strong radical-mediated magnetic coupling in multimetallic complexes. These results demonstrate the potential of radical-bearing tritopic HITP ligands as building blocks for extended molecule-based magnetic materials.

Dimensionality Modulates Electrical Conductivity in Compositionally Constant One-, Two-, and Three-Dimensional Frameworks.

We reveal here the construction of Ni-based metal-organic frameworks (MOFs) and conjugated coordination polymers (CCPs) with different structural dimensionalities, including closely π-stacked 1D chains (), aggregated 2D layers (), and a 3D framework (), based on 2,3,5,6-tetraamino-1,4-hydroquinone (TAHQ) and its various oxidized forms. These materials have the same metal-ligand composition but exhibit distinct electronic properties caused by different dimensionalities and supramolecular interactions between SBUs, ligands, and structural motifs. The electrical conductivity of these materials spans nearly 8 orders of magnitude, approaching 0.

Cytidine acetylation yields a hypoinflammatory synthetic messenger RNA.

Synthetic messenger RNA (mRNA) is an emerging therapeutic platform with important applications in oncology and infectious disease. Effective mRNA medicines must be translated by the ribosome but not trigger a strong nucleic acid-mediated immune response. To expand the medicinal chemistry toolbox for these agents, here we report the properties of the naturally occurring nucleobase N-acetylcytidine (ac4C) in synthetic mRNAs.