Inorganic Nanorods Enable the Memorization of Photoinduced Microlens Arrays in Dye-Doped Liquid Crystals.

The photoinduced molecular reorientation of liquid crystals (LCs) caused by their nonlinear optical responses has attracted much attention due to their large refractive index change, leading to promising applications in optical devices. This reorientation is typically induced by light irradiation above a threshold intensity and is temporary, with the initial orientation recovering unless the LCs are polymerized and cross-linked. Our report highlights the memory effect of molecular reorientation in LCs.

Insights into Chemical Bonding Modes and Heat Transport at the Molecular Level.

Despite the demand for nanoscale thermal management technologies of material surfaces and interfaces using organic molecules, heat transport properties at the single molecular level remain elusive due to the experimental difficulty of measuring temperature at the nanoscopic scale. Here we show how chemical bonding modes can affect the heat transport properties of single molecules. We focused on four molecular systems: benzylthiol linked to another phenyl group by either a triple (compound ), double (), or amide () bond and a common linear alkanethiol (), all of which are nearly identical in molecular length.

Covalent Bonds van der Waals Forces: A Picture in Thermal Conduction of Organic Materials.

We present a direct comparison of the heat transport properties between the state in which the constituent molecules are assembled by intermolecular forces and the one in which they are covalently bonded, in a molecular system with identical constituent elements and masses, as well as a nearly identical structure and density. This comparison leading to an essential understanding of thermal conduction in organic materials is made possible by the unique compound found by Wudl et al., which exhibits a single-crystal-to-single-crystal topochemical polymerization with a yield of >99%, in combination with microtemperature wave analysis (TWA), which allows accurate measurements of the thermal diffusivity of small single crystals.

Supramolecular scaffold-directed two-dimensional assembly of pentacene into a configuration to facilitate singlet fission.

Molecular assemblies featuring two-dimensionality have attracted increasing attention, whereas such structures are difficult to construct simply relying on spontaneous molecular assembly. Here, we present two-dimensional assemblies of acene chromophores achieved using a tripodal triptycene supramolecular scaffold, which have been shown to exhibit a strong ability to assemble molecular and polymer motifs two-dimensionally. We designed pentacene and anthracene derivatives sandwiched by two triptycene units.

Peripheral Fusion of Carbon-Based Aromatic Rings to BN-Heteropentalene Leading to Close π-Stacking in the Solid State.

π-Electronic molecules with a BN-heterocyclic and carbon-based aromatic hybrid ring system (h-CBN) are interesting in that they potentially exhibit synergistic properties arising from the two different π-systems. Here we report the synthesis and properties of a h-CBN-type molecule (1) having a bicyclic BN-heteropentalene core fused with extended aromatic rings. This molecule exhibits excellent chemical stability despite the absence of bulky substituents for kinetic protection, which in turn provides effective stacking of the π-system upon crystallization.

2D hexagonal assembly of a dipolar rotor with a close interval of 0.8 nm using a triptycene-based supramolecular scaffold.

Controlling the rotation of carbon-carbon bonds, which is ubiquitous in organic molecules, to create functionality has been a subject of interest for a long time. In this context, it would be interesting to explore whether cooperative and collective rotation could occur if dipolar molecular rotors were aligned close together while leaving adequate space for rotation. However, it is difficult to realize such structures as bulk molecular assemblies, since molecules generally tend to assemble into the closest packing structure to maximize intermolecular forces.

Phosphonic acid anchored tripodal molecular films on indium tin oxide.

Whereas monopodal self-assembling monolayers (SAMs) are most frequently used for surface and interface engineering, tripodal SAMs are less popular due to the difficulty in achieving a reliable and homogeneous bonding configuration. In this context, in the present study, the potential of phosphonic acid (PA) decorated triptycene (TripPA) for formation of SAMs on oxide substrates was studied, using indium tin oxide (ITO) as a representative and application-relevant test support. A combination of several complementary experimental techniques was applied and a suitable monopodal reference system, benzylphosphonic acid (PPA), was used.

Triple Isomerism in 3D Covalent Organic Frameworks.

Isomerism in covalent organic frameworks (COFs) has scarcely been known. Here, for the first time we show 3D COFs with three framework isomers or polymorphs constructed from the same building blocks. All isomers were obtained as large (>10 μm) crystals; although their crystal shapes were distinctly different, they showed identical FT-IR and solid-state NMR spectra.

Synthesis and Characterization of Side-Chain Liquid-Crystalline Block Copolymers Containing Cyano-Terminated Phenyl Benzoate Moieties.

Block copolymers, known for their capacity to undergo microphase separation, spontaneously yield various periodic nanostructures. These precisely controlled nanostructures have attracted considerable interest due to their potential applications in microfabrication templates, conducting films, filter membranes, and other areas. However, it is crucial to acknowledge that microphase-separated structures typically exhibit random alignment, making alignment control a pivotal factor in functional material development.

Potential reasons for failure and recurrence in microvascular decompression for hemifacial spasm.

Background: To examine the factors contributing to persistent and recurrent hemifacial spasms (HFS) following a microvascular decompression (MVD) procedure and to suggest technical improvements to prevent such failures.

Methods: A retrospective review was conducted on fifty-two cases of repeat surgery. The extent of the previous craniotomy and the location of neurovascular compression (NVC) were investigated.

Skeletal rearrangement of a boron-containing annulenic molecule into a macrocycle bridged by an electronically stabilized boron cation.

An annulenic molecule containing a three-coordinate chloroborane moiety, which exhibits a borane-olefin proximity effect, undergoes a skeletal rearrangement upon chloride abstraction, to generate a three-dimensional macrocyclic molecule featuring a borocenium (η-cyclopentadienyl-B-R) structure.

Radical resection of intracavernous chondrosarcoma using an intradural keyhole approach: how I do it.

Background: Skull base chondrosarcoma is rare, arising from the clivus or petroclival junction, and usually presents as ocular motility disorders. Endonasal transsphenoidal surgery may be performed in some cases of midline clivus chondrosarcoma. Chondrosarcoma is located within the cavernous sinus and presents a softer/gelatinous mass and can be removed with suctions and curettage.

Insights into Thermal Transport through Molecular π-Stacking.

π-Stacking, which is a ubiquitous structural motif in assemblies of aromatic compounds, is well-known to provide a transport pathway for charge carriers and excitons, while its contribution to thermal transport is still unclear. Herein, based on detailed experimental observations of the thermal diffusivity, thermal conductivity, and specific heat of a single-crystalline triphenylene featuring a one-dimensionally π-stacked structure, we describe the nature of thermal transport through the π-stacked columns. We reveal that acoustic phonons are responsible for thermal transport through the π-stacked columns, which exhibit crystal-like behavior.

Inversion of Diaza[5]Helicenes Through an N-N Bond Breaking Pathway.

1,1',10,10'-Biphenothiazine and its S,S,S',S'-tetroxide are diaza[5]helicenes with N-N linkages. Kinetic experiments on racemization together with DFT calculations revealed that they undergo inversion through the N-N bond breaking pathway rather than the general conformational pathway. In these diaza[5]helicenes with this inversion mechanism, the reduction of electronic repulsion in the N-N bond by modification of S to SO at the outer position of the helix led to a significantly higher inversion barrier, 35.

Collective bending motion of a two-dimensionally correlated bowl-stacked columnar liquid crystalline assembly under a shear force.

Stacked teacups inspired the idea that columnar assemblies of stacked bowl-shaped molecules may exhibit a unique dynamic behavior, unlike usual assemblies of planar disc- and rod-shaped molecules. On the basis of the molecular design concept for creating higher-order discotic liquid crystals, found in our group, we synthesized a sumanene derivative with octyloxycarbonyl side chains. This molecule forms an ordered hexagonal columnar mesophase, but unexpectedly, the columnar assembly is very soft, similar to sugar syrup.

Overcoming the entropy of polymer chains by making a plane with terminal groups: a thermoplastic PDMS with a long-range 1D structural order.

Due to its unique physical and chemical properties, polydimethylsiloxane (PDMS) is widely used in many applications, in which covalent cross-linking is commonly used to cure the fluidic polymer. The formation of a non-covalent network achieved through the incorporation of terminal groups that exhibit strong intermolecular interactions has also been reported to improve the mechanical properties of PDMS. Through the design of a terminal group capable of two-dimensional (2D) assembly, rather than the generally used multiple hydrogen bonding motifs, we have recently demonstrated an approach for inducing long-range structural ordering of PDMS, resulting in a dramatic change in the polymer from a fluid to a viscous solid.

Synthesis and Properties of B N -Heteropentalenes Fused with Polycyclic Hydrocarbons.

Hybrid molecules of π-conjugated carbon rings and BN-heterocyclic rings (h-CBNs) fused with each other have been a rare class of compounds due to the limited availability of their synthetic methods. Here we report the synthesis of new h-CBNs featuring a B N -heteropentalene core and polycyclic aromatic hydrocarbon wings. Using 1,2-azaborinine derivatives as a building block, we developed a rational synthetic protocol that allows the formation of a B N ring in a stepwise manner, resulting in the fully fused ABA-type triblock molecules.

Surface Passivation of Lead Halide Perovskite Solar Cells by a Bifacial Donor-π-Donor Molecule.

Surface passivation is key to the power conversion efficiency (PCE) of organic-inorganic lead halide perovskite solar cells (PSCs). Herein, we report a novel molecular concept of a -symmetric -type bifacial donor-π-donor (D-π-D) passivation molecule (a racemic mixture of enantiomers) with hydrophobic phenyls and hydrophilic tetraethylene glycol-substituted phenyls on each face of the indeno-[1,2-]fluorene π-core. In addition to this bifacial amphiphilic π-core unit, triphenylamine, a well-established passivation donor, effectively passivated the PSC surface, facilitated hole transfer, and increased the maximum PCE from 18.

Indication for a skull base approach in microvascular decompression for hemifacial spasm.

Background: A thorough observation of the root exit zone (REZ) and secure transposition of the offending arteries is crucial for a successful microvascular decompression (MVD) for hemifacial spasm (HFS). Decompression procedures are not always feasible in a narrow operative field through a retrosigmoid approach. In such instances, extending the craniectomy laterally is useful in accomplishing the procedure safely.

Design of discotic liquid crystal enabling complete switching along with memory of homeotropic and homogeneous alignment over a large area.

The alignment control of discotic columnar liquid crystals (LCs), featuring a low motility of the constituent molecules and thus having a large viscosity, is a challenging task. Here we show that triphenylene hexacarboxylic ester, when functionalized with hybrid side chains consisting of alkyl and perfluoroalkyl groups in an appropriate ratio, gives a hexagonal columnar (Col) LC capable of selectively forming large-area uniform homeotropic or homogeneous alignments, upon cooling from its isotropic melt or upon application of a shear force at its LC temperature, respectively. In addition to the alignment switching ability, each alignment state remains persistent unless the LC is heated to its melting temperature.

Factors affecting global neurocognitive status and frontal executive functions in the early stage after surgical clipping of unruptured anterior circulation aneurysms with respect to keyhole clipping and conventional clipping.

Purpose: This study investigated the most significant factor for the preservation of the global neurocognitive status and frontal executive functions in the surgical clipping of unruptured anterior circulation aneurysms, specifically in keyhole and conventional clipping procedures.

Methods: The prospective study that was performed to examine the effects of aneurysm surgery on the patient's global neurocognitive status and frontal executive functions started on April 2016. After exclusion posterior circulation aneurysms, anterior communicating aneurysms treated by interhemispheric approach, giant aneurysms, and paraclinoid aneurysms, 23 patients who were enrolled before May 2017 were treated by conventional clipping, and 18 patients who were enrolled after June 2017 were treated by keyhole clipping.

Introduction of Triptycene with a Particular Substitution Pattern into Polymer Chains Can Dramatically Improve the Structural and Rheological Properties.

Although a large number of polymers that contain triptycene units in the main chains have been developed, no polymer design using 1,8-substituted triptycene has been reported to date. In this study, we investigated the properties of linear homo- and copolymers obtained by ring-opening polymerization of a triptycene monomer bearing a macrocyclic olefin linked at its 1,8-position and its copolymerization with cyclooctene, respectively. We found that the introduction of triptycene with this substitution pattern leads to nanoscale molecular ordering, thereby greatly improving the physical properties of the polymers.

Histology of the Porous Oculomotorius: Relevance to Anterior Skull Base Approaches.

 Mobilization of cranial nerve III (CNIII) at its dural entry site is commonly described to avoid damage from stretching during approaches to the parasellar, infrachiasmatic, posterior clinoid, and cavernous sinus regions. The histologic relationships of CNIII as it traverses the dura, and the associated surgical implications are nonetheless poorly described. We herein assess the histology of the CNIII-dura interface as it relates to surgical mobilization of the nerve.