On the Fundamental Polymer Chemistry of Inverse Vulcanization for Statistical and Segmented Copolymers from Elemental Sulfur

In this concept review, the fundamental and polymerization chemistry of inverse vulcanization for the preparation of statistical and segmented sulfur copolymers, which have been actively developed and advanced in various applications over the past decade is discussed. This concept review delves into a discussion of step-growth polymerization constructs to describe the inverse vulcanization process and discuss prepolymer approaches for the synthesis of segmented sulfur polyurethanes. Furthermore, this concept review discusses the advantages of inverse vulcanization in conjunction with dynamic covalent polymerization and post-polymerization modifications to prepare segmented block copolymers with enhanced thermomechanical and flame retardant properties of these materials.     

Secondary Metabolites of Litchi chinensis

Chemistry of Natural Compounds -     

Subdominant H60 antigen-specific CD8 T-cell response precedes dominant H4 antigen-specific response during the initial phase of allogenic skin graft rejection

In allogeneic transplantation, including the B6 anti-BALB.B settings, H60 and H4 are two representative dominant minor histocompatibility antigens that induce strong CD8 T-cell responses. With different distribution patterns, H60 expression is restricted to hematopoietic cells, whereas H4 is ubiquitously expressed. H60-specific CD8 T-cell response has been known to be dominant in most cases of B6 anti-BALB.B allo-responses, except in the case of skin transplantation. To understand the mechanism underlying the subdominance of H60 during allogeneic skin transplantation, we investigated the dynamics of the H60-specific CD8 T cells in B6 mice transplanted with allogeneic BALB.B tail skin. Unexpectedly, longitudinal bioluminescence imaging and flow cytometric analyses revealed that H60-specific CD8 T cells were not always subdominant to H4-specific cells but instead showed a brief dominance before the H4 response became predominant. H60-specific CD8 T cells could expand in the draining lymph node and migrate to the BALB.B allografts, indicating their active participation in the anti-BALB.B allo-response. Enhancing the frequencies of H60-reactive CD8 T cells prior to skin transplantation reversed the immune hierarchy between H60 and H4. Additionally, H60 became predominant when antigen presentation was limited to the direct pathway. However, when antigen presentation was restricted to the indirect pathway, the expansion of H60-specific CD8 T cells was limited, whereas H4-specific CD8 T cells expanded significantly, suggesting that the temporary immunodominance and eventual subdominance of H60 could be due to their reliance on the direct antigen presentation pathway. These results enhance our understanding of the immunodominance phenomenon following allogeneic tissue transplantation.     

Unsymmetrical Pyrene‐Fused Phthalocyanine Derivatives: Synthesis,Structure, and Properties

Novel pyrene‐fused unsymmetrical phthalocyanine derivatives 2,3,9,10,16,17‐hexakis(2,6‐dimethylphenoxy)‐22,25‐diaza(2,7‐di‐tert‐butylpyrene)[4,5]phthalocyaninato zinc complex Zn[Pc(Pz‐pyrene)(OC₈H₉)₆] ( 1 ) and 2,3,9,10‐tra(2,6‐dimethylphenoxy)‐15,18,22,25‐traza(2,7‐di‐tert‐butylpyrene)[4,5]phthalocyaninato zinc compound Zn[Pc(Pz‐pyrene)₂(OC₈H₉)₄] ( 2 ) were isolated for the first time. These unsymmetrical pyrene‐fused phthalocyanine derivatives have been characterized by a wide range of spectroscopic and electrochemical methods. In particular, the pyrene‐fused phthalocyanine structure was unambiguously revealed on the basis of single crystal X‐ray diffraction analysis of 1 , representing the first structurally characterized phthalocyanine derivative fused with an aromatic moiety larger than benzene.     

Path to achieving molecular dispersion in a dense reactive mixture

A uniform dispersion of reactants is necessary to achieve a complete reaction involving multicomponents. In this study, we have examined the role of plasticizer in the reaction of two seemingly unlikely reactants: a highly crystalline hexamethylenetetramine (HMTA) and a strongly hydrogen bonded phenol formaldehyde resin. By combining information from NMR, infrared spectroscopy and differential scanning calorimetry, we were able to determine the role of specific intermolecular interactions necessary for the plasticizer to dissolve the highly crystalline HMTA and to plasticize the phenol formaldehyde resin in this crosslinking reaction. The presence of the plasticizer increased the segmental mobility, disrupted the hydrogen bonded matrix, and freed the hydroxyl units, which further increased the solubility of the HMTA. Both the endothermic and exothermic transitions are accounted for in the calorimetric data obtained. For the first time, it is possible to obtain the effective molar ratio of each component needed to complete the crosslinking reaction efficiently. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1519–1526     

Bis-tridentate IrIII Phosphors Bearing Two Fused Five-Six-Membered Metallacycles: A Strategy to Improved Photostability of Blue Emitters

Iridium complexes bearing chelating cyclometalates are popular choices as dopant emitters in the fabrication of organic light-emitting diodes (OLEDs). In this contribution, we report a series of blue-emitting, bis-tridentate Ir^III complexes bearing chelates with two fused five-six-membered metallacycles, which are in sharp contrast to the traditional designs of tridentate chelates that form the alternative, fused five-five metallacycles. Five Ir^III complexes, Px-21 – 23 , Cz-4 , and Cz-5 , have been synthesized that contain a coordinated dicarbene pincer chelate incorporating a methylene spacer and a dianionic chromophoric chelate possessing either a phenoxy or carbazolyl appendage to tune the coordination arrangement. All these tridentate chelates afford peripheral ligand–metal–ligand bite angles of 166–170°, which are larger than the typical bite angle of 153–155° observed for their five-five-coordinated tridentate counterparts, thereby leading to reduced geometrical distortion in the octahedral frameworks. Photophysical measurements and TD-DFT studies verified the inherent transition characteristics that give rise to high emission efficiency, and photodegradation experiments confirmed the improved stability in comparison with the benchmark fac-[Ir(ppy)₃] in degassed toluene at room temperature. Phosphorescent OLED devices were also fabricated, among which the carbazolyl-functionalized emitter Cz-5 exhibited the best performance among all the studied bis-tridentate phosphors, showing a maximum external quantum efficiency (EQE_max) of 18.7 % and CIE_x,y coordinates of (0.145, 0.218), with a slightly reduced EQE of 13.7 % at 100 cd m⁻² due to efficiency roll-off.     

Dynamic Variation of Excitonic Coupling in Excited Bilayer Graphene Quantum Dots?

The intermolecular interaction determines the photophysical properties of the organic aggregates, which are critical to the performance of organic photovoltaics. Here, excitonic coupling, an important intermolecular interaction in organic aggregates, between the π-stacking graphene quantum dots is studied by using transient absorption spectroscopy. We find that the spectral evolution of the ground state bleach arises from the dynamic variation of the excitonic coupling in the excited π-stacks. According to the spectral simulations, we demonstrate that the kinetics of the vibronic peak can be exploited as a probe to measure the dynamics of excitonic coupling in the excited π-stacks.     

Theoretical analysis of dynamic behaviors of cable-stayed bridges excited by two harmonic forces

Nonlinear Dynamics - To better understand the dynamic behaviors of cable-stayed bridges, this study investigates the dynamic behaviors of a cable-stayed shallow arch subjected to two external...