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. The resulting data consistently show that TripPA forms well-defined, densely packed, and nearly contamination-free tripodal SAMs on ITO, with the similar parameters and properties as the monopodal reference system. Modification of wetting properties and work function of ITO by non-substituted and cyano-decorated TripPA SAMs was demonstrated, showing a potential of this tripodal system for surface engineering of oxide substrates.

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. Our structural analyses revealed unprecedented triple isomerism in 3D COFs (noninterpenetrated dia, qtz, and 3-fold interpenetrated dia-c3 nets). Furthermore, this Communication reports the first known COF with qtz topology for which the structure determination was based on Rietveld analysis. We achieved triple framework isomerism by reticulating a tetrahedral building block with a flexible junction and a linear building block with PEO side chains and by varying solution compositions. Our energy calculations, along with the discovery of interisomer transition, revealed that the isomer with qtz topology was a kinetic isomer. Thus, this simple yet little-explored concept of reticulating only flexible building blocks is an effective pathway to significantly broaden the diversity of 3D COFs, which have been proposed for a myriad of applications.

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. To address this challenge, researchers have explored the use of block copolymers containing liquid-crystalline (LC) polymers, which offer a promising technique for alignment control. The molecular structure and LC behavior of these polymers significantly impact the morphology and alignment of microphase-separated structures. In this study, we synthesized LC diblock copolymers with cyano-terminated phenyl benzoate moieties and evaluated the microphase-separated structures and molecular alignment behaviors. The LC diblock copolymers with a narrow molecular weight distribution were synthesized by atom transfer radical polymerization. Small angle X-ray scattering measurements revealed that the block copolymers exhibit smectic LC phases and form cylinder structures with a lattice period of about 18 nm by microphase separation. The examination of block copolymer films using polarized optical microscopy and polarized UV-visible absorption spectroscopy corroborated that the LC moieties were uniaxially aligned along the alignment treatment direction.

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. The operative findings were categorized into two groups: "Missing Compression" and "Teflon Contact". The analysis included long-term outcomes and operative complications after repeat MVD procedures. RESULTS: Missing compression was identified in 29 patients (56%), while Teflon contact was observed in 23 patients (44%). Patients with missing compression were more likely to experience improper craniotomy (66%) compared to those with Teflon contact (48%). Medially located NVC was a frequent finding in both groups, mainly due to compression by the anterior inferior cerebellar artery. In the missing compression group, during the repeat MVD, Teflon sling retraction was utilized in 79% of cases, while in the Teflon contact group, the most common procedure involved removing the Teflon in contact (65%). After the repeat MVD procedure, immediate spasm relief was achieved in 42 patients (81%), with six (12%) experiencing delayed relief. After a median follow-up of 54 months, 96% of patients were free from spasms. Delayed facial palsy, facial weakness, and hearing impairment were more frequently observed in the Teflon contact group. CONCLUSIONS: A proper craniotomy that provides adequate exposure around the REZ is crucial to prevent missing the culprit vessel during the initial MVD procedure. Teflon contact on the REZ should be avoided, as it poses a potential risk of procedure failure and recurrence.

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 (η5-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. We have been using a simple intradural keyhole transcavernous approach, avoiding a complex extradural transcavernous dissection. METHODS: The intracavernous chondrosarcoma was removed via a 5 mm keyhole opening over the Parkinson's triangle using a standard frontotemporal intradural approach. CONCLUSION: Minimally invasive keyhole surgical resection can be performed to eradicate skull base chondrosarcomas, avoiding complex extradural cranial base approaches.

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. Importantly, the thermal energy stored as intramolecular vibrations can also be transported by coupling to the acoustic phonons. In contrast, in the direction perpendicular to the π-stacked columns, an amorphous-like thermal transport behavior dominates. The present finding offers deep insight into nanoscale thermal transport in organic materials, where the constituent molecules exist as discrete entities linked together by weak intermolecular interactions.

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

Objective 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. Methods A fronto-orbitozygomatic temporopolar approach was performed on six adult cadaveric specimens. The CNIII-dural entry site was resected and histologically processed. The nerve-tissue planes were assessed by a neuropathologist. Results Histologic analysis demonstrated that CNIII remained separate from the dura within the oculomotor cistern (porous oculomotorius up to the oculomotor foramen). Fusion of the epineurium of CNIII and the connective tissue of the dura was seen at the level of the foramen, with no clear histologic plane identified between these structures. Conclusion CNIII may be directly mobilized within the oculomotor cistern, while dissections of CNIII distal to the oculomotor foramen should maintain a thin layer of connective tissue on the nerve.

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 SO2 at the outer position of the helix led to a significantly higher inversion barrier, 35.3 kcal/mol, compared to [5]helicene. 1,1',10,10'-Biphenothiazine S,S,S',S'-tetroxide was highly resistant to acid-mediated N-N bond breaking and racemization under acidic conditions.

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. It displays, upon application of a shear force on solid substrates, a flexible bending motion with continuous angle variations of bowl-stacked columns while preserving the two-dimensional hexagonal order. In general, alignment control of higher-order liquid crystals is difficult to achieve due to their high viscosity. The present system that brings together higher structural order and mechanical softness will spark interest in bowl-shaped molecules as a component for developing higher-order liquid crystals with unique mechanical and stimuli-responsive properties.

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. Here we present an even more surprising terminal-group effect: simply replacing a hydrogen with a methoxy group leads to extraordinary enhancement of the mechanical properties, giving rise to a thermoplastic PDMS material without covalent cross-linking. This finding would update the general notion that less polar and smaller terminal groups barely affect polymer properties. Based on a detailed study of the thermal, structural, morphological and rheological properties of the terminal-functionalized PDMS, we revealed that 2D assembly of the terminal groups results in networks of PDMS chains, which are arranged as domains with long-range one-dimensional (1D) periodic order, thereby increasing the storage modulus of the PDMS to exceed its loss modulus. Upon heating, the 1D periodic order is lost at around 120 °C, while the 2D assembly is maintained up to ∼160 °C. The 2D and 1D structures are recovered in sequence upon cooling. Due to the thermally reversible, stepwise structural disruption/formation as well as the lack of covalent cross-linking, the terminal-functionalized PDMS shows thermoplastic behavior and self-healing properties. The terminal group presented herein, which can form a 'plane', might also drive other polymers to assemble into a periodically ordered network structure, thereby allowing for significant modulation of their mechanical properties.

Synthesis and Properties of B4 N4 -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 B4 N4 -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 B4 N4 ring in a stepwise manner, resulting in the fully fused ABA-type triblock molecules. Thus, three derivatives of 1 bearing naphthalene (1Naph ), anthracene (1Anth ), or phenanthrene (1Phen ) wings fused with the B4 N4 core were synthesized and characterized. Among them, 1Phen , which displays the highest triplet-state energy, was found to serve a host material for phosphorescent OLED devices, for which a maximum external quantum efficiency of 13.7 % was recorded. These findings may promote the synthesis of various types of h-CBNs aiming at new properties arising from the synergy of two different π-electronic systems.

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 C2-symmetric syn-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-b]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 18.43 to 19.74%. Another notable effect is the removal of remnant PbI2 and the change in the perovskite orientation on the surface by the syn-type molecule. In contrast, the anti-type isomer degraded its long-term stability. We characterized the electrostatic and electronic properties of these molecules and highlighted the advantage of molecular strategy based on a bifacial structure and its stereochemistry.

3,11-Diaminodibenzo[a,j]phenazine: Synthesis, Properties, and Applications to Tröger's Base-Forming Ladder Polymerization.

A new class of diamino-substituted π-extended phenazine compound was synthesized, and its photophysical properties were investigated. The U-shaped diaminophenazine displayed photoluminescence in solution with moderate quantum yield. The diamino aromatic compound was found applicable to the poly-condensation with formaldehyde to form Tröger's base ladder polymer. The obtained microporous ladder polymer features high CO2 adsorption selectivity against N2 , most likely due to the presence of basic nitrogen atoms in the phenazine rings.

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. This study aims to introduce the benefits of a skull base approach in MVD for HFS. METHODS: The skull base approach was performed in twenty-eight patients among 335 consecutive MVDs for HFS. The site of the neurovascular compression (NVC), the size of the flocculus, and the location of the sigmoid sinus are measured factors in the imaging studies. The indication for a skull base approach is evaluated and verified retrospectively in comparison with the conventional retrosigmoid approach. Operative outcomes and long-term results were analyzed retrospectively. RESULTS: The extended retrosigmoid approach was used for 27 patients and the retrolabyrinthine presigmoid approach was used in one patient. The measurement value including the site of NVC, the size of the flocculus, and the location of the sigmoid sinus represents well the indication of the skull base approach, which is significantly different from the conventional retrosigmoid approach. The skull base approach is useful for patients with medially located NVC, a large flocculus, or repeat MVD cases. The long-term result demonstrated favorable outcomes in patients with the skull base approach applied. CONCLUSIONS: Preoperative evaluation for lateral expansion of the craniectomy contributes to a safe and secure MVD.

Gross Total Resection of a Recurrent Cavernous Sinus Meningioma through a Combined Transzygomatic Transcavernous and Extended Middle Fossa Approach with Cavernous Carotid Denudation.

Objective The aim of this study is to describe surgical management of invasive cavernous sinus meningioma with a combination of skull base approaches. Design This study is an operative video. Results Resection of the recurrent skull base meningioma is still challenging, especially if the tumor involves or encases the carotid artery. In this video, we describe our experience with the successful treatment of a recurrent skull base meningioma, which involved the entire cavernous sinus and the internal carotid artery. A 53-year-old male presented with a 1-year history of progressing right-side complete oculomotor palsy and facial dysesthesia. The patient had previously undergone craniotomy for the right-side petroclival cavernous meningioma ( Fig. 1A and B ). Total 8 years after the first surgery, the remaining portion of the cavernous sinus grew up and extended into the posterior fossa ( Fig. 1C ). Then the second surgery was performed to resect only the posterior fossa component ( Fig. 1D ). However, the follow-up magnetic resonance imaging revealed an aggressive tumor regrowth in 2 years. The tumor occupied the right middle fossa with an extension to the posterior fossa and infratemporal fossa ( Fig. 1E and F ). We scheduled to perform gross total resection of the tumor through a combined transzygomatic transcavernous and extended middle fossa approach with preparation for vessel reconstruction. Mild adhesion between the tumor and the cavernous carotid artery facilitated complete resection of the intracavernous component of the tumor ( Fig. 2A-C ). Conclusion A combination of skull base approaches provides multidirectional operative corridors and wide exposure of the skull base lesions. The link to the video can be found at https://youtu.be/DB_WXFeyBvo .

Gross Total Resection of a Recurrent in-and-around Cavernous Sinus Meningioma through a Combined Transcavernous Anterior and Middle Infratemporal Fossa Approach with Extracranial-Intracranial Bypass.

Objectives The study aims to describe surgical management of an invasive cavernous sinus meningioma with a combination of several skull base approaches and bypass surgery. Design This study is an operative video. Results Resection of the recurrent skull base meningioma is still challenging, especially if the tumor involves or encases the carotid artery. Cerebral bypass surgery is an essential adjunct in the armamentarium of skull base surgery when vessel reconstruction is required. In this paper, we describe our experience of successful treatment of an invasive recurrent skull base meningioma, which involved the entire cavernous sinus and the internal carotid artery. A 46-year-old woman presented with a 2-year history of gradually worsening left-sided exophthalmos and visual impairment. The patient had previously undergone two craniotomies for resection of the left-sided spheno-orbital meningioma. Pathological diagnosis was chordoid meningioma, which is classified as an intermediate-grade meningioma. The second surgery had been performed for a rapid tumor regrowth 6 months after the first surgery. The patient lost her left-side vision after the second surgery. Aggressive tumor regrowth was confirmed with extension into the left orbit, infratemporal fossa, and cavernous sinus with engulfment of the carotid artery. A balloon occlusion test revealed intolerance of the left internal carotid artery occlusion. Considering the patient's age, tumor behavior, and intolerance of the carotid artery of the lesion side, we scheduled gross total resection of the tumor with vessel reconstruction. Conclusion Although cerebral bypass surgery is a technically challenging procedure, it plays an important role in the surgical management of the complex vessel-engulfing tumor. The link to the video can be found at https://youtu.be/GCmpxK3hW18 .

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 (Colh) 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. In situ X-ray diffraction analysis under the application of a shear force, together with polarized optical microscopy observations, revealed how the columnar assembly is changed during the alignment-switching process. The remarkable behavior of the discotic LC is discussed in terms of its rheological properties.

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. Two patients were excluded from each group due to missing data. Finally, 21 and 16 patients in each group were analyzed, respectively. Three-tesla magnetic resonance imaging was performed before and after surgery to detect the presence of perioperative cerebral infarctions and brain edema. The Mini-Mental State Examination, Frontal Assessment Battery, and Self-Rating Depression Scale scores were obtained before and 1 month after surgery. RESULTS: Logistic regression analyses indicated that anterior communicating and internal carotid artery aneurysms were the most significant factors for poor outcomes and that keyhole clipping for these two types of aneurysm was the most significant factor for the preservation of patient global neurocognitive status. Keyhole clipping was also the most significant factor for the preservation of frontal executive functions in patients. CONCLUSIONS: Keyhole clipping may be more favorable than conventional clipping for the preservation of the global neurocognitive status and frontal executive functions. Moreover, it may be the most effective factor for preservation of global neurocognitive status when it is indicated for anterior communicating or internal carotid artery aneurysms.

A carbon-functionality-appended diborylacetylene available for a component of organic synthesis and OLEDs.

We present new 1,2-diborylacetylene derivatives with planar 9-oxa-10-boraanthracene termini, which display excellent stability to allow usual handling and even thermal evaporation for the preparation of thin films for OLEDs, and also undergo typical reactions of alkynes such as the Diels-Alder reaction.