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Assessing Tumor-Infiltrating Lymphocytes in Breast Cancer Utilizing Preoperative MRI-Based Radiomics.
The TPSA/VB12-DETA-Gly nanoparticles were nontoxic and exhibited targeted endocytosis for the Caco-2 cells, and showed high permeation through intestinal enterocytes using the Caco-2 cell model. Therefore, they exhibit potential for enhancing the absorption efficacy of tea polysaccharides through the small intestinal mucosa.The prediction of optical spectra of complex solids remains a great challenge for first-principles calculations due to the huge computational cost of the state-of-the-art many-body perturbation theory based GW-Bethe Salpeter equation (BSE) approach. An alternative method is the time-dependent density-functional theory (TDDFT) based on hybrid exchange-correlation functionals, which involves the essential ingredients of electron-hole interactions in its formalism in contrast to its local/semi-local functional counterparts. In this work, we investigate the optical absorption spectra of ceria (CeO2), a prototypical lanthanide oxide with a 4f0 configuration, utilizing TDDFT based on four well-established hybrid functionals for ground state DFT calculations. All four functionals reproduce well the excitonic features of the experimental optical spectra, in spite of the significant differences in their band structures arising from different hybridization parameters (i.e. the fraction of the Hartree-Fock exchange and the screening parameter). It is demonstrated that the apparently weak dependence of the resulting optical spectra on the employed functionals is quite universal and applies to simple semiconductors such as Si and GaAs and insulator LiF as well. This study highlights the feasibility of TDDFT based on existing hybrids to describe optical spectra of solids, and also, points out the difficulty of obtaining accurate exciton binding energies using these hybrid functionals due to the strong functional dependence of quasi-particle band structures.Correction for 'A short PEG linker alters the in vivo pharmacokinetics of trastuzumab to yield high-contrast immuno-PET images' by Woonghee Lee et al., J. Mater. Chem. B, 2021, 9, 2993-2997, DOI 10.1039/D0TB02911D.The construction of cooperative systems comprising several units is an essential challenge for artificial systems toward the development of sophisticated functions comparable to those found in biological systems. Flexible frameworks possessing various functional groups that can form weak intra/intermolecular interactions similar to those observed in biological systems have promising design features for artificial systems used to control cooperative systems. However, it is difficult to construct multiple component systems >1 nm using these flexible units by controlling the arrangement of functional units, beginning with the precise control of the cooperative switching of multiple units. In general, it is difficult for oligopeptides to form stable conformations by themselves, although they have designability and structural features suitable for the development of cooperative systems. Increasing the number of coordination bonds in peptides, which are stronger than hydrogen bonds, can be used to control the assembled peptide structures and stabilize their structures owing to the variety of coordination bonds and selective binding affinity. Thus, metal complexes of artificial short peptides have great potential for the development of multicomponent cooperative systems. Based on this concept, we have developed a series of novel metal complexes of flexible peptides and have achieved, to date, cooperative systems, the formation of giant structures, and precise control over the functional units that are the essential bases for designable multifunctional systems that can be regarded as artificial enzymes. In this feature article, we summarize these results and discuss the principal/essential design of artificial systems.We describe new container host molecules - deep cavitands with benzimidazole walls and ionic feet - to recognize highly hydrophilic guest molecules in water. The aromatic surfaces of the cavity recognize hydrophobic portions of the guest while bound water molecules mediate hydrogen bonding in the complex. Spectroscopic (NMR) evidence indicates slow in/out exchange on the chemical shift timescale and thermodynamic (ITC) methods show large association constants (Ka up to 6 × 104 M-1) for complexation of small, water-soluble molecules such as THF and dioxane. Quantum chemical calculations are employed to optimize the host-guest geometries and elucidate the hydrogen bonding patterns responsible for the binding.Two-dimensional piezoelectric materials have attracted great attention as they could play a vital role in nano-electromagnetic systems. Herein, we investigate the compelling piezoelectric properties of Janus ZrSeO in monolayer and bulk structures using density functional theory calculations with a van der Waals correction. One of the two independent out-of-plane piezoelectric coefficients (e31) of the bulk ZrSeO is as high as 287.60 pC m-1, which is over five times larger than that of monolayer ZrSeO due to charge changes in the internal structure within each Zr, Se, and O layer. Interestingly, another large negative out-of-plane piezoelectric stress coefficient (e33) of bulk ZrSeO (-467.40 pC m-1) results from the displacement difference between the electronic and ionic center positions, which is at least three times larger than those previously reported for Janus Mo/W/Hf-based transition metal dichalcogenides. The charge transformation between atoms under strain induces negative piezoelectric stress, a process that is clarified using maximally localized Wannier functions (MLWF) and Bader charge analysis. This research also reveals the dependence of piezoelectricity in Janus MXY on the metal (M = Zr, Hf, W, Mo) and chalcogenide (X,Y = S, Se, O) components, which are directly proportional to the electronegativity and the atomic size difference.Kaolinite particles are geometrically anisometric and electrostatically anisotropic. Until recently, the charge of both basal faces of kaolinite was assumed to be independent of pH, and the isoelectric point (IEP) of the edge surface was thought to occur at pH 4-6. Therefore, kaolinite suspensions were expected to have an edge-face association at low pH. However, recent atomic force microscopy (AFM) studies have shown that the kaolinite alumina basal face and edge surface carry a pH-dependent surface charge with an IEP at pH 5-6 and ∼ 3, respectively. Here, we revisit the modes of particle association in kaolinite suspensions and apply Derjaguin-Landau-Verwey-Overbeek (DLVO) theory to study the rheological implications of surface charges of various kaolinite faces from recent AFM-based studies. Specifically, aging within the linear viscoelastic region, small amplitude oscillatory shear behavior (strain amplitude and frequency response), and critical stress behavior were studied as a function of pH. Kaolinite suspensions (40 wt%) exhibited two-step structure recovery after shear rejuvenation and two-step yielding at pH less than the IEP of the alumina basal face. In addition, the storage modulus (G') and critical stress required to stabilize the flow followed non-monotonic behavior as a function of pH. At low pH, the silica face-alumina face mode of association was expected to be dominant rather than the edge-face microstructure. A peak in the G'vs. pH curve at pH 4.5-5 was correlated with the silica face-alumina face attraction estimated from DLVO theory, which passes through a maximum at approximately the same pH. Based on these observations, we propose a qualitative state diagram for kaolinite suspensions in the pH-concentration space.Glass-forming liquids are well known to have significant dynamic heterogeneities, leading to spatially grossly varying elastic properties throughout the system. In this paper, we compare the local elastic response of supercooled 1-propanol monitored by triplet state solvation dynamics to the macroscopic dynamic shear modulus measured by a piezo-electric gauge. The time-dependent responses are found to be identical, which means that the dynamic macroscopic shear modulus provides a good measure of the average local elastic properties. Since the macroscopic shear modulus of a dynamically inhomogeneous system in general is not just the average of the local moduli, there was no reason to expect such a result. This surprising finding not only provides constraints for models of dynamical heterogeneities in glass-forming liquids, but also allows for a fairly straightforward check on elastic models for glassy dynamics.Heparin (Hep) is a highly negatively charged linear glycosaminoglycan involved in various physiological processes, especially blood coagulation. Hep is also a first-line drug for anticoagulation and prevention of thromboembolism, but its overdose will cause serious side effects. Herein, we designed a long-wavelength double-charged cationic fluorescent probe PYPN, and studied its aggregation state and detection performance for Hep. PYPN was readily synthesized through a one-step reaction without complicated purification. B102 In aqueous medium, PYPN molecules with an amphiphilic structure spontaneously form nano-assemblies, which can be immediately decomposed by Hep due to the formation of a PYPN-Hep complex based on electrostatic attraction. The assembly shows a fast, sensitive and ratiometric fluorescence response to Hep, without being obviously interfered by other compounds. In various serum matrices, the fluorescence intensity ratio F610/F470 has a good linearity with Hep concentration (0-12 μg mL-1), and the detection limit (0.11-0.12 U mL-1) is lower than the minimum concentration (0.2 U mL-1) used in clinical treatment. Our study provides an easy-to-prepare and feasible tool for the selective and sensitive quantification of Hep in serum.Selection of monomer couples, ensuring reactivity ratios close to zero, is an effective strategy to induce spontaneous copolymerization into an alternating sequence. In addition, monomer design and customisation of the solvent-monomer interactions open the way to functional copolymers showing molecular self-assembly relevant to their regular amphipathic structure. In this work, we show that the design of comonomers with adequate reactivities and interactions can be used to direct copolymer self-assembly on a mesoscopic scale. We investigate spontaneous formation of nanoparticles through solvent/non-solvent interactions using the so-called "ouzo effect". In this way, an ouzo diagram was built to determine the operation window for the self-assembly, in aqueous suspensions, of alternating copolymers consisting of vinyl phenol and maleimide units carrying long alkyl-pendant groups (C12H25 or C18H37). Also, investigations were pursued to account for the influence of the lateral lipophilic pendant units on the size and structure of the nanoaggregates formed during one-shot water addition. Structure characterisation by light scattering techniques (DLS and SLS), small-angle neutron scattering (SANS) and transmission electron microscopy (cryo-TEM and TEM) confirmed the self-assembly of copolymer chains into nanoparticles (size range 60-300 nm), the size of which is affected by the lipophilicity of the alternating copolymers, solvent-water affinity and the solvent diffusion in water. Altogether, we present here the spontaneous ouzo effect as a simple method to produce stable alternating copolymer nanoparticles in water without the addition of stabilizing agents.
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