Crystallization-Induced Chirality Transfer in Conformationally Flexible Azahelicene Au(I) Complexes with Circularly Polarized Luminescence Activation.

Flexible and twisted annulated π-systems exhibit numerous unique and desirable features, owing to their ability to display chirality. However, preventing their racemization due to the dynamic nature of their chirality remains a challenge. One promising approach to stabilize homochirality in such systems is chirality transfer from a chiral auxiliary to a moiety displaying dynamic chirality. Herein, we introduce a new approach for dynamic chirality stabilization in conformationally flexible azahelicene species via crystallization-induced intermolecular chirality transfer in Au(I) complexes featuring azahelicene (dibenzo[c,g]carbazole and benzo[c]carbazole) and enantio-pure chiral N-heterocyclic carbene (NHC) ligands with a complementary tailored shape. Crystallization of these azahelicene Au(I) complexes not only suppresses the dynamic chirality of the dibenzocarbazole species but also stabilizes their homochirality through the intermolecular conjunction between the chiral NHC and dibenzocarbazole ligands. In the Au(I) benzocarbazole complexes, the intermolecular conjunction and chirality transfer in the crystals induce chirality in the initially achiral benzocarbazole ligand. Furthermore, the crystallization of the studied complexes activates their circularly polarized luminescence (CPL) properties, which were suppressed in solution. Importantly, chirality transfer leads to significant CPL enhancement; the complexes that feature chirality transfer within the crystal structure exhibit luminescence dissymmetry factors 5 to 10 times higher than those of the complexes without chirality transfer.

Ring Expansion of Cyclic Boronates via Oxyboration of Arynes.

The oxyboration of arynes was achieved for the first time. A series of 2-aryl-1,3,2-dioxaborolane derivatives were reacted with aryne precursors in the presence of CsF to give the corresponding ring-expanded seven-membered borinic acid esters via selective boron-oxygen bond activation. Preliminary experimental mechanistic studies and density functional theory (DFT) calculations suggest that this unprecedented aryne oxyboration proceeds through the formation of boron ate complexes of arylboronates with CsF, followed by aryne insertion into the boron-oxygen bond.

Using Mechanochemistry to Activate Commodity Plastics as Initiators for Radical Chain Reactions of Small Organic Molecules.

Radical initiators such as azo compounds and organic peroxides have been widely used to facilitate numerous transformations of free radicals, which enable the efficient synthesis of structurally complex molecules, natural products, polymers, and functional materials. However, these high-energy reagents are potentially explosive and thus often require special precautions or delicate operating conditions. We postulated that a more convenient and safer alternative for radical chain initiation could be developed by mechanical activation of thermodynamically stable covalent bonds. Here, we show that commodity plastics such as polyethylene and poly(vinyl acetate) are capable of acting as efficient initiators for radical chain reactions under solvent-free mechanochemical conditions. In this approach, polymeric mechanoradicals, which are generated by homolytic cleavage of the polymer chains in response to the applied mechanical energy provided by ball milling, react with tris(trimethylsilyl)silane to initiate radical chain dehalogenation of organic halides. Preliminary calculations support our proposed force-induced radical chain mechanism.

Mechanochemical Synthesis of Non-Solvated Dialkylalumanyl Anion and XPS Characterization of Al(I) and Al(II) Species.

A non-solvated alkyl-substituted Al(I) anion dimer was synthesized by a reduction of haloalumane precursor using a mechanochemical method. The crystallographic and theoretical analysis revealed its structure and electronic properties. Experimental XPS analysis of the Al(I) anions with reference compounds revealed the lower Al 2p binding energy corresponds to the lower oxidation state of Al species. It should be emphasized that the experimentally obtained XPS binding energies were reproduced by delta SCF calculations and were linearly correlated with NPA charges and 2p orbital energies.

Relationship between assistant's lens exposure and dose information during computed tomography examinations.

According to International Commission of Radiological Protection, the equivalent dose limit for the eye lens for occupational exposure is recommended to be 20 mSv yr-1, averaged over 5 years, with no single year above 50 mSv. Some studies reported the measurement of assistant's lens exposure in diagnostic computed tomography (CT) examinations, but further investigation is still required in the association between the lens dose for assistants and various dose parameters. Therefore, we measured the assistant's lens exposure using small optically stimulated luminescence dosimeters. The type of occupation, type of assistance, total scan time, total mAs, total scan length, and dose-length product (DLP) were recorded and analyzed in association with air kerma at the lens position. The assistance was classified into four types: 'assisted ventilation,' 'head holding,' 'body holding,' and 'raising patient's arm.' The air kerma of lens position was not significantly different for each assistance type (p< 0.05, Kruskal-Wallis test). Further, the lens doses for assistants correlated with DLP, but with various strengths of correlation with the assistance type and were influenced by the distance from the CT gantry. In conclusion, lens dose during assistance and DLP demonstrated the strongest correlation. 'Raising patient's arm' and 'head holding' exhibited stronger correlations, which required less table movement during the CT scan than 'assisted ventilation' and 'body holding'.

Iterative Synthesis of Oligosilanes Using Methoxyphenyl- or Hydrogen-Substituted Silylboronates as Building Blocks: A General Synthetic Method for Complex Oligosilanes.

Organosilanes have attracted the attention of researchers for more than 150 years due to their unique properties, and they have become indispensable industrial assets. However, many synthesized oligosilanes with multiple Si-Si bonds are relatively simple, i.e., they often only contain a single repeating unit. More laborious customized synthetic routes can lead to more complex oligosilanes, but compared to carbon-based molecules, their structural diversity remains limited. The development of effective and practical synthetic routes to complex oligosilanes that contain mixed substituents constitutes a long-standing challenge. Here, we describe an iterative synthesis of oligosilanes using methoxyphenyl- or hydrogen-substituted silylboronates, which were obtained via transition-metal-catalyzed Si-H borylation reactions. The first key reaction is a cross-Si-Si bond-forming reaction between chloro(oligo)silanes and silylboronates activated by MeLi. The second key reaction is the selective chlorination of the methoxyphenyl group or the hydrogen atom at the terminal of the oligosilanes. Iteration of these two key reactions enables the synthesis of various oligosilanes that are otherwise difficult to access. As a demonstration of the synthetic utility of this iterative synthetic approach, oligosilanes with different sequences were prepared by simply changing the order of the reaction of four different silicon units. Furthermore, a bespoke tree-shaped oligosilane is easily obtained via the present iterative synthesis. The solid-state structures of several of these oligosilanes were unequivocally determined using single-crystal X-ray diffraction analysis.

Mechanochemistry-Directed Ligand Design: Development of a High-Performance Phosphine Ligand for Palladium-Catalyzed Mechanochemical Organoboron Cross-Coupling.

Mechanochemical synthesis that uses transition-metal catalysts has attracted significant attention due to its numerous advantages, including low solvent waste, short reaction times, and the avoidance of problems associated with the low solubility of starting materials. However, even though the mechanochemical reaction environment is largely different from that of homogeneous solution systems, transition-metal catalysts, which were originally developed for use in solution, have been used directly in mechanochemical reactions without any molecular-level modifications to ensure their suitability for mechanochemistry. Alas, this has limited the development of more efficient mechanochemical cross-coupling processes. Here, we report a conceptually distinct approach, whereby a mechanochemistry-directed design is used to develop ligands for mechanochemical Suzuki-Miyaura cross-coupling reactions. The ligand development was guided by the experimental observation of catalyst deactivation via the aggregation of palladium species, a problem that is particularly prominent in solid-state reactions. By embedding the ligand into a poly(ethylene glycol) (PEG) polymer, we found that phosphine-ligated palladium(0) species could be immobilized in the fluid phase created by the PEG chains, preventing the physical mixing of the catalyst into the crystalline solid phase and thus undesired catalyst deactivation. This catalytic system showed high catalytic activity in reactions of polyaromatic substrates close to room temperature. These substrates usually require elevated temperatures to be reactive in the presence of catalyst systems with conventional ligands such as SPhos. The present study hence provides important insights for the design of high-performance catalysts for solid-state reactions and has the potential to inspire the development of industrially attractive, almost solvent-free mechanochemical cross-coupling technologies.

In Situ and Real-Time Visualization of Mechanochemical Damage in Double-Network Hydrogels by Prefluorescent Probe via Oxygen-Relayed Radical Trapping.

Visualization of mechanochemical damages, especially for those in the molecular-scale (e.g., bond scission in polymeric materials), is of great industrial and academic significance. Herein, we report a novel strategy for in situ and real-time visualization of mechanochemical damages in hydrogels by utilizing prefluorescent probes via oxygen-relayed free-radical trapping. Double-network (DN) hydrogels that generate numerous mechanoradicals by homolytic bond scission of the brittle first network at large deformation are used as model materials. Theoretical calculation suggests that mechanoradicals generated by the damage of the first network undergo an oxygen-relayed radical-transfer process which can be detected by the prefluorescent probe through the radical-radical coupling reaction. Such an oxygen-relayed radical-trapping process of the prefluorescent probe exhibits a dramatically enhanced emission, which enables the real-time sensing and visualization of mechanochemical damages in DN hydrogels made from brittle networks of varied chemical structures. To the best of authors' knowledge, this work is the first report utilizing oxygen as a radical-relaying molecule for visualizing mechanoradical damages in polymer materials. Moreover, this new method based on the probe post-loading is simple and does not introduce any chemical structural changes in the materials, outperforming most previous methods that require chemical incorporation of mechanophores into polymer networks.

A Steric-Repulsion-Driven Clutch Stack of Triaryltriazines: Correlated Molecular Rotations and a Thermoresponsive Gearshift in the Crystalline Solid.

We report that a newly developed type of triaryltriazine rotor, which bears bulky silyl moieties on the para position of its peripheral phenylene groups, forms a columnar stacked clutch structure in the crystalline phase. The phenylene units of the crystalline rotors display two different and interconvertible correlated molecular motions. It is possible to switch between these intermolecular geared rotational motions via a thermally induced crystal-to-crystal phase transition. Variable-temperature solid-state 2H NMR measurements and X-ray diffraction studies revealed that the crystalline rotor is characterized by a vertically stacked columnar structure upon introducing a bulky Si moiety with bent geometry as the stator. The structure exhibits correlated flapping motions via a combination of 85° and ca. 95° rotations between 295 and 348 K, concurrent with a negative entropy change (ΔS‡ = -23 ± 0.3 cal mol-1 K-1). Interestingly, heating the crystal beyond 348 K induces an anisotropic expansion of the column and lowers the steric congestion between the adjacent rotators, thus altering the correlated motions from a flapping motion to a correlated 2-fold 180° rotation with a lower entropic penalty (ΔS‡ = -14 ± 0.5 cal mol-1 K-1). The obtained results of our study suggest that the intermolecular stacking of the C3-symmetric rotator driven by the steric repulsion of the bulky stator represents a promising strategy for producing various correlated molecular motions in the crystalline phase. Moreover, direct and reversible modulation of the intermolecularly correlated rotation is achieved via a thermally induced crystal-to-crystal phase transition, which operates as a gearshift function at the molecular level.

Solid-state cross-coupling reactions of insoluble aryl halides under polymer-assisted grinding conditions.

In this study, polymer-assisted grinding (POLAG), a ball-milling technique based on the use of polymer additives, was applied to mechanochemical solid-state Suzuki-Miyaura cross-coupling reactions of insoluble aryl halides. We found that the efficiency of this challenging solid-state cross-coupling was improved by the addition of polytetrafluoroethylene (PTFE) as a POLAG additive under high-temperature ball-milling conditions. Our results suggest that POLAG is a promising approach for controlling the reactivity of insoluble substrates that are barely reactive under conventional solution-based conditions.

Eye lens dose for medical staff assisting patients during computed tomography: comparison of several types of radioprotective glasses.

Medical staff sometimes assists patients in the examination room during computed tomography (CT) scans for several purposes. This study aimed to investigate the dose reduction effects of four radioprotective glasses with different lead equivalents and lens shapes. A medical staff phantom was positioned assuming body movement restraint of the patient during chest CT, and Hp(3) at the eye surfaces of the medical staff phantom and inside the lens of the four types of radioprotective glasses were measured by changing the distance of the staff phantom from the gantry, eye height, and width of the nose pad. The Hp(3) at the right eye surface with glasses of 0.50-0.75 mmPb and 0.07 mmPb was approximately 83.5% and 58.0%, respectively, lower than that without radioprotective glasses. The dose reduction rates at left eye surface increased with over-glass type glasses by 14%-28% by increasing the distance from the CT gantry to the staff phantom from 25 to 65 cm. The dose reduction rates at the left eye surface decreased with over-glass type glasses by 26%-31% by increasing the height of the eye lens for the medical staff phantom from 130 to 170 cm. The Hp(3) on the left eye surface decreased by 46.9% with the widest nose pad width compared to the narrowest nose pad width for the glasses with adjustable nose pad width. The radioprotective glasses for staff assisting patients during CT examinations should have a high lead equivalent and no gap around the nose and under the front lens.

Dual Nickel(II)/Mechanoredox Catalysis: Mechanical-Force-Driven Aryl-Amination Reactions Using Ball Milling and Piezoelectric Materials.

The combination of a nickel(II) catalyst and a mechanoredox catalyst under ball-milling conditions promotes mechanical-force-driven C-N cross-coupling reactions. In this nickel(II)/mechanoredox cocatalyst system, the modulation of the oxidation state of the nickel center, induced by piezoelectricity, is used to facilitate a highly efficient aryl-amination reaction, which is characterized by a broad substrate scope, an inexpensive combination of catalysts (NiBr2 and BaTiO3 ), short reaction times, and an almost negligible quantity of solvents. Moreover, this reaction can be readily up-scaled to the multi-gram scale, and all synthetic operations can be carried out under atmospheric conditions without the need for complicated reaction setups. Furthermore, this force-induced system is suitable for excitation-energy-accepting molecules and poorly soluble polyaromatic substrates that are incompatible with solution-based nickel(II)/photoredox cocatalysts.

Mechanochemical Approach for Air-Tolerant and Extremely Fast Lithium-Based Birch Reductions in Minutes.

Birch reduction has been widely used in organic synthesis for over half a century as a powerful method to dearomatize arenes into 1,4-cyclohexadiene derivatives. However, the conventional Birch reduction reaction using liquid ammonia requires laborious procedures to ensure inert conditions and low temperatures. Although several ammonia-free modifications have been reported, the development of an operationally simple, efficient, and scalable protocol remains a challenge. Herein, we report an ammonia-free lithium-based Birch reduction in air without special operating conditions using a ball-milling technique. This method is characterized by its operational simplicity and an extremely short reaction time (within 1 min), probably owing to the in situ mechanical activation of lithium metal, broad substrate scope, and no requirement for dry bulk solvents. The potential of our flash Birch reaction is also demonstrated by the efficient reduction of bioactive target molecules and gram-scale synthesis.

Giant Crystalline Molecular Rotors that Operate in the Solid State.

Molecular motion in the solid state is typically precluded by the highly dense environment, and only molecules with a limited range of sizes show such dynamics. Here, we demonstrate the solid-state rotational motion of two giant molecules, i.e., triptycene and pentiptycene, by encapsulating a bulky N-heterocyclic carbene (NHC) Au(I) complex in the crystalline media. To date, triptycene is the largest molecule (surface area: 245 Å2 ; volume: 219 Å3 ) for which rotation has been reported in the solid state, with the largest rotational diameter among reported solid-state molecular rotors (9.5 Å). However, the pentiptycene rotator that is the subject of this study (surface area: 392 Å2 ; volume: 361 Å3 ; rotational diameter: 13.0 Å) surpasses this record. Single-crystal X-ray diffraction analyses of both the developed rotors revealed that these possess sufficient free volume around the rotator. The molecular motion in the solid state was confirmed using variable-temperature solid-state 2 H spin-echo NMR studies. The triptycene rotor exhibited three-fold rotation, while temperature-dependent changes of the rotational angle were observed for the pentiptycene rotor.

Acromiohumeral distance changes with posture in healthy adults and patients while wearing a shoulder abduction brace.

[Purpose] To examine the humeral head positions while wearing an abduction brace in the sitting and supine positions in healthy adults and patients who have been operated on for shoulder joint diseases. [Participants and Methods] Thirty participants were included in the study, of which 15 were healthy adults (without any orthopedic diseases) and 15 had shoulder diseases (post-arthroscopic repair of a rotator cuff tear). The acromion and humeral head were observed on ultrasound. The acromiohumeral distance was measured once in two different positions while wearing the brace: edge sitting and supine. [Results] The mean acromiohumeral distance in the healthy group was 7.9 ± 1.1 mm while sitting and 7.2 ± 1.0 mm in the supine position. In the disease group it was 7.6 ± 0.9 mm while sitting and 6.3 ± 1.1 mm in the supine position. Multiple logical regression revealed that the acromiohumeral distance was not affected by the participant's age, height, or weight. [Conclusion] The acromiohumeral distance was significantly reduced in the supine position despite the use of an abduction brace. Therefore, patients must use a pillow/towel to support the shoulder joint to prevent unnecessary stress while the cuff tendons are healing.

Conformationally Fixed Chiral Bisphosphine Ligands by Steric Modulators on the Ligand Backbone: Selective Synthesis of Strained 1,2-Disubstituted Chiral cis-Cyclopropanes.

A new series of C1-symmetric P-chirogenic bisphosphine ligands of the type (R)-5,8-Si-Quinox-tBu3 (Silyl = SiMe3, SiEt3, SiMe2Ph) have been developed. The bulky silyl modulators attached to the ligand backbone fix the phosphine substituents to form rigid chiral environments that can be used for substrate recognition. The ligand showed high performances for a copper(I)-catalyzed asymmetric borylative cyclopropanation of bulky silyl-substituted allylic electrophiles to afford higher disfavored 1,2-cis-silyl-boryl-cyclopropanes than the other possible isomers, trans-cyclopropane and allylboronate (up to 97% yield; 98% ee; cis/trans = >99:1; cyclopropane/allylboronate = >99:1). Detailed computational studies suggested that the highly rigid phosphine conformation, which is virtually undisturbed by the steric interactions with the bulky silyl-substituted allyl electrophiles, is key to the high stereo- and product-selectivities. Furthermore, the detailed computational analysis provided insight into the mechanism of the stereoretention or -inversion of the chiral alkylcopper(I) intermediate in the intramolecular cyclization.

Distinct Fold-Mode Formation of Crystalline Cu(I) Helical Coordination Polymers with Alternation of the Solid-State Emission Using Shape of the Counter Anions.

One-dimensional cationic coordination polymers have been a promising platform for designing solid-state physical properties through diverse coordination geometries. In particular, the folding mode of the coordination polymers that form a helical structure directly determines the metal-centered coordination environment. Herein, we report N-heterocyclic carbene (NHC) Cu(I) cationic coordination polymers with pyrazine as the linker, which construct a 4-fold or 3-fold helical column in luminescent crystals using octahedral anions (SbF6- and PF6-) or a tetrahedral anion (BF4-), respectively. Single-crystal XRD studies revealed that the folding modes depend on the structural shape of the counteranions, which form H-F interactions between ligands and anions. Indeed, the folding mode change from 4-fold to 3-fold by including a different shape of the counteranions, resulting in red-shifted emission from approximately 580 to 687 nm, which is difficult to modulate in the solid state.

Usefulness of a lead-acrylic shield for reducing lens dose of assistant in x-ray CT examination.

In computed tomography (CT) examinations, the usefulness of protective glasses for reducing lens exposure to assistants has been reported. The present study aimed to compare the dose reduction effect for assistants with lead-acrylic shields and protective glasses (0.07 mm Pb, 0.5 mm Pb) during CT examination. The air dose distribution in a CT examination room with and without a lead-acrylic shield was compared. It was found that the amount of scattered radiation was significantly reduced by installing a lead-acrylic shield at the CT gantry aperture. Moreover, the reduction rate of air kerma at the assistant's lens was higher using the lead acrylic shield than with the protective glasses-95.7% during head holding and 76.1% during assisted ventilation.

Mechanochemically Generated Calcium-Based Heavy Grignard Reagents and Their Application to Carbon-Carbon Bond-Forming Reactions.

In sharp contrast to the use of conventional magnesium-based Grignard reagents (R-MgX), the application of calcium-based heavy Grignard reagents (R-CaX) in organic synthesis remains poorly explored. This is mainly due to the lack of experimentally simple ways to access such organocalcium nucleophiles from readily available starting materials under mild conditions. Here, we show that a mechanochemical technique using ball milling allows the generation of calcium-based heavy Grignard reagents from aryl halides and commercially available calcium metal without complicated pre-activation processes. Notably, all experimental operations can be carried out in air. Our operationally simple protocol enables the rapid development of novel cross-electrophile-coupling reactions mediated by arylcalcium nucleophiles, which are rather difficult using conventional Grignard reagents. This method will allow synthetic chemists to readily access the novel and unique reactivity of organocalcium nucleophiles.

Palladium-catalyzed solid-state borylation of aryl halides using mechanochemistry.

This study describes the solid-state palladium-catalyzed cross-coupling between aryl halides and bis(pinacolato)diboron using ball milling. The reactions were completed within 10 min for most aryl halides to afford a variety of synthetically useful arylboronates in high yields. Notably, all experimental operations could be performed in air, and did not require the use of large amounts of dry and degassed organic solvents. The utility of this method was further demonstrated by gram-scale synthesis under solvent-free, mechanochemical conditions.