Lasing in Low-Dimensional Crystals of a Fumaronitrile-Based Luminogen.

Low-dimensional structures are ideal for organic laser media because of their efficient waveguide, photon confinement, and stimulated emission. Control of the structure and alignment of luminescent molecules is very important for realizing laser media. Here, we fabricate low-dimensional crystals of bis(biphenyl)fumaronitrile (BPFN), which is an aggregation-induced emission luminogen. The BPFN molecule contains fumaronitrile, which displays solid-state luminescence, and biphenyl, which forms low-dimensional structures through dipole-dipole interactions. Solvent diffusion yielded two-dimensional platelet crystals of BPFN with strong dipole-dipole CH-π interactions. The high photoluminescence quantum efficiency of 0.46 and uniaxially aligned molecular π-electronic transition dipole moment in the two-dimensional crystals of BPFN resulted in optically pumped lasing even when using an optical excitation source with a long pulse duration (∼5 ns). One-dimensional BPFN crystals obtained via epitaxial growth on the cleaved surface of a KBr single crystal also displayed lasing behavior.

Phase Diagrams of Anthracene Derivatives in Pyridinium Ionic Liquids.

Crystal engineering for single crystallization of π-conjugated molecules has attracted much attention because of their electronic, photonic, and mechanical properties. However, reproducibility is a problem in conventional printing techniques because control of solvent evaporation is difficult. We investigated the phase diagrams of two anthracene derivatives in synthesized ionic liquids for non-volatile crystal engineering to determine the critical points for nucleation and crystal growth. Anthracene and 9,10-dibromoanthracene were used as representative π-conjugated molecules that form crystal structures with different packing types. Ionic liquids with an alkylpyridinium cation and bis(fluorosulfonyl)amide were good solvents for the anthracene derivatives from ca. 0 °C to 200 °C. The solubilities (critical points for crystal growth) of the anthracene derivatives in the ionic liquids reached the 100 mM level, which is similar to those in organic solvents. Ionic liquids with phenyl and octyl groups tended to show high-temperature dependence (a high dissolution entropy) with 9,10-dibromoanthracene. The precipitation temperature (critical point for crystal nucleation) at each 9,10-dibromoanthracene concentration was lower than the dissolution temperature. The differences between the dissolution and precipitation temperatures (supersaturated region) in the ionic liquids were greater than those in an organic solvent.

Giant Seebeck effect over 0.1 V K-1 - is this an intrinsic phenomenon in organic semiconductors?

A good solution for energy harvesting is to generate electricity using waste heat from our bodies or living environment. Therefore, the development of flexible and lightweight thermoelectric generators (TEGs) is urgently necessary, and studies on organic thermoelectric materials have become increasingly intensive. This article will present ongoing studies about a mysterious phenomenon in organic semiconductors, the giant Seebeck effect (GSE). The GSE was first discovered with pure C60 thin films and eventually confirmed to occur in various organic semiconductors. In the thin films or single crystals of organic small-molecule semiconductors with high purity, i.e., small carrier density, huge Seebeck coefficients, >0.1 V K-1, were reproducibly observed in the temperature range near 300-400 K. The facts revealed by the experiments to date will be presented, and unresolved mysteries will be discussed.

Systematic Order-Made Synthesis of Sequence-Defined Polyurethanes with Length, Types, and Topologies.

Polyurethanes are industrially and academically important as soft materials. They are conventionally synthesized by a process based on step-growth polymerization; thus, molecular weight and structural control are impossible. However, the development of a synthetic strategy for polyurethanes remains a big challenge in designing soft materials. Herein, we demonstrate a synthetic methodology for generating polyurethanes with selectable lengths and termini characteristics. The multistep synthetic process offered the systematic synthesis of high-molecular weight, regioregular, and α,ω-urethane telechelics. Various oligomers with order-made repeating units revealed the effective length of the polymer properties. To demonstrate the scope of our methodology, it was also applied to the synthesis of block co-oligomers, three-armed star oligomers, and miktoarm star co-oligomers. Thus, our method allows the synthesis of high-molecular-weight oligomers with complete structural and molecular weight control, which is of enormous value to materials science; particularly the study and application of structure-property relationships in polyurethanes.

Noninvasive Three-dimensional Assessment of Single Molecular Crystals Using Multiphoton Microscopic Observation and Their Deformation-induced Emission Characteristics.

Distinguishing the luminescence contribution from the surface and bulk of a crystal is a long-standing challenge in crystal materials. Herein, three-dimensional, multiphoton, luminescence microscope imaging of the elastic molecular single crystal 1,4-bis(4-methylthien-2-yl)-2,3,5,6-tetrafluorobenzene, was conducted. Further, the luminescence contribution from the surface and bulk of the crystal was experimentally distinguished. Strong luminescence was observed only from the surface of the crystal, while the bulk did not emit strongly. Furthermore, the surface and bulk luminescence behavior responded well to the mechanical shape change of the crystal; i.e., strong luminescence was observed for the elongated side of the crystal.

Flexible and Red-Emissive Organic Single-Crystal Microresonator for Efficient Active Waveguides.

We fabricated a flexible and red-emissive microcrystal resonator for highly efficient optical waveguiding. The microfiber crystals of diketopyrrolopyrrole (DPP) used in this work possess a high photoluminescence (PL) quantum efficiency (ΦPL = 0.45) and exhibit a micromechanical deformation shape in the curved state. The crystals show optical fringes in their PL spectra, suggesting the existence of a naturally formed Fabry-Pérot crystal resonator owing to its flat crystal surface. The group refractive index (ng) and Rabi splitting energy (ℏΩ) indicating the coupling strength between excitons and resonator photons are large (ng = 3.7-6.0, â„Ω = 1.38 eV), suggesting the strong confinement of waveguiding photons. Spatially resolved PL measurements revealed that the PL in a crystal fiber is efficiently waveguided, even in a curved crystal with a very small curvature radius of 11 µm. Strong photon confinement inside a crystal resonator is a plausible origin of efficient optical waveguiding.

Non-Covalent Supramolecular 1D Alternating Copolymer in Crystal toward 2D Anisotropic Photon Transport.

To realize organic integrated optoelectronic circuits, there is a need for anisotropic optical waveguides at the micro/nanoscale. Anisotropic alignment of one-dimensional-ordered supramolecular structures composed of light-emissive π-conjugated molecules in a crystal may meet the requirements of such waveguides. Here, a bipyridyl-appended acrylonitrile-based π-conjugated molecule was designed, which produced a one-dimensional supramolecular polymer constructed through non-covalent bonding between a lone pair in bipyridyl and a σ-hole in 1,4-diiodo-2,3,5,6-tetrafluorobenzene. The one-dimensional copolymer of bipyridyl and 1,4-diiodo-2,3,5,6-tetrafluorobenzene is aligned horizontally with the two-dimensional crystal surface because of the angle-controlled supramolecular synthons. As a result of control over the non-covalent bonding direction, anisotropic photoluminescence and photon transport (optical waveguiding) characteristics are realized by orienting the transition dipole moment horizontally with respect to the two-dimensional surface. Compared with the loss coefficient αL =52 dB cm-1 for the long-axis direction of the two-dimensional platelet cocrystal, a very large difference of αS =2111 dB cm-1 is present in the crystal short-axis direction. The anisotropic waveguiding ability, αL /αS , is estimated to be 41, which is more than an order of magnitude greater than previously reported two-dimensional platelet crystal waveguides. This supramolecular synthon provides an approach to designing anisotropic photon transporters and highly regulated optical logic circuits.

Gasless laparoendoscopic single-site assisted extracorporeal ovarian cystectomy through the umbilicus for the management of ovarian torsion at 33 weeks of gestation: A case report with literature review.

Ovarian torsion in the third trimester of pregnancy is a rare but potentially dangerous non-obstetric complication for both mother and fetus and presents a diagnostic and therapeutic challenge for the treating physicians. A 39-year-old woman (gravida 2, para 1) presented at 7 weeks of gestation. Asymptomatic bilateral small ovarian cysts were diagnosed at the initial presentation. Progesterone was intramuscularly administered every 2 weeks after 28 weeks of gestation because of uterine cervical length shortening. Sudden onset of right lateral abdominal pain was reported at 33 weeks and 2 days of gestation. Emergency laparoendoscopic single-site (LESS) surgery was performed through the umbilicus under strong suspicion of right adnexal torsion with ovarian cyst, as indicated by magnetic resonance imaging a day after admission. Isolated right ovarian torsion without fallopian tube involvement was identified under laparoscopic view. The contents of the right ovarian cyst were aspirated after confirming resumption of color tone of the right ovary after detorsion. Then, the right adnexal tissue was grasped through the umbilicus, followed by a successful ovarian cystectomy under direct vision. Tocolysis was postoperatively attempted by intravenous ritodorine hydrochloride and magnesium sulfate administration, which was continued through to 36 weeks and 4 days of gestation, because of increased uterine contraction frequency. The next day, spontaneous labor occurred, followed by the vaginal delivery of a healthy 2108-g female infant. The postnatal course was uneventful. Transumbilical LESS-assisted extracorporeal ovarian cystectomy is a feasible and minimally invasive option for ovarian torsion management in the third trimester of pregnancy.

Elastic and bright assembly-induced luminescent crystals of platinum(II) complexes with near-unity emission quantum yield.

Molecular crystals of Pt(II) complexes with metallophilic interactions can provide bright assembly-induced luminescence with colour tunability. However, the brittleness of many of these crystals makes their application in flexible optical materials difficult. Herein, we have achieved the elastic deformation of crystals of polyhalogenated Pt(II) complexes exhibiting bright assembly-induced luminescence. A crystal of [Pt(bpic)(dFppy)] (Hbpic = 5-bromopicolinic acid, HdFppy = 2-(2,4-difluorophenyl)pyridine) and a co-crystal of [Pt(bpic)(dFppy)] and [Pt(bpic)(ppy)] (Hppy = 2-phenylpyridine) were found to exhibit significant elastic deformation due to their highly anisotropic interaction topologies. While the crystal of [Pt(bpic)(dFppy)] exhibited monomer-based ligand-centred 3ππ* emission with an emission quantum yield of 0.40, the co-crystal exhibited bright, triplet metal-metal-to-ligand charge transfer (3MMLCT) emission owing to Pt⋯Pt interactions, thereby achieving a significantly higher emission quantum yield of 0.94.

Structural Phase Transitions in Anthracene Crystals.

Invited for this month's cover is the collaborating group of Prof. Shotaro Hayashi at Kochi University of Technology. The cover picture shows anthracene molecules depicted among sakura blossoms at Kochi University of Technology (KUT). Anthracenes are arranged with falling petals, giving a beautiful image of the molecular crystal engineering field. The cover was designed by Yuto Hino. More information can be found in the Review by S. Hayashi and co-workers.

Diluted aqueous extract of heat-not-burn tobacco product smoke causes less oxidative damage in fibroblasts than conventional cigarette.

Smoke from conventional cigarettes (C-cigarettes) contains various reactive oxygen species and toxic chemicals, which potentially cause oxidative damage not only to airways but also to the whole body, leading eventually to diseases, including emphysema, advanced atherosclerosis, and cancer. Many heat-not-burn tobacco products (HTPs) have been commercialized recently in Japan to maintain the smoking population by advertising that HTPs are less toxic. However, there were few studies reported from neutral organizations whether HTPs are indeed less damaging. To evaluate the potential capacity of HTPs to induce oxidative stress, we here compared two different HTPs with two types of C-cigarettes, using human fibroblast IMR90SV cells and 5% aqueous extracts in 10-ml phosphate-buffered saline (50-ml smoke/10 s). HTPs exhibited significantly lower oxidative toxicity in comparison to C-cigarettes. Whereas C-cigarettes induced ferroptosis in fibroblasts, the effects of HTPs were significantly reduced by measuring the levels of peroxides, pro-inflammatory cytokine expression, autophagy, catalytic Fe(II) and 8-hydroxy-2'-deoxyguanosine. Notably, major portions of C-cigarettes-induced pathogenic responses were inhibited by catalase. However, HTPs still induced p62 autophagy-adaptor at 5%-dilution and caused lethal effects to fibroblasts with undiluted solution. In conclusion, HTPs smoke per se can be toxic despite less toxicity in comparison to C-cigarettes, which warrants further investigation.

Structural Phase Transitions in Anthracene Crystals.

Anthracene (C14 H10 ) and its derivatives, π-conjugated molecules in acenes, have been widely researched in terms of their reactions, physical properties, and self-assembly (or crystal engineering). These molecules can be functionalized to tune reactivities, optoelectronic properties, and self-assembling abilities. Structural changes in the molecular assemblies, solid states, and crystals have recently been discovered. Therefore, a systematic discussion of anthracene's molecular structure, packing, and optical properties based on its intermolecular structure and phase transitions is important for future chemical and structural design. In the present review, we discuss anthracene's molecular design, dimer packing, and crystal structure, focusing on the structural phase transitions of its crystals. We also provide examples of the phase transitions of anthracene crystals. Changes to edge-to-face of CH-π interaction and face-to-face packing of π-π interaction affect the thermodynamic stabilities of various crystal structures. These structures can inform the prediction of structural and physical properties.

Effectiveness of NLRP3 Inhibitor as a Non-Hormonal Treatment for ovarian endometriosis.

BACKGROUND: Endometriosis is a complex syndrome characterized by an estrogen-dependent chronic inflammatory process that affects 10% of women of reproductive age. Ovarian endometriosis (OE) is the most common lesion in endometriosis and may cause infertility, in addition to dysmenorrhea. Hormonal treatments, which are the conventional treatment methods for endometriosis, suppress ovulation and hence are not compatible with fertility. The inflammasome is a complex that includes Nod-like receptor (NLR) family proteins, which sense pathogen-associated molecular patterns and homeostasis-altering molecular processes. It has been reported that the nucleotide-binding oligomerization domain, leucine-rich repeat, and pyrin domain-containing (NLRP) 3 inflammasome, which contributes to the activation of interleukin-1 beta (IL-1ß), might be related to the progression of endometriosis. Therefore, the aim of the present study was to evaluate non-hormonal therapies for OE, such as inhibitors of the NLRP3 inflammasome. METHODS: The expression of NLRP3 was measured in the eutopic endometrium (EM) of patients with and without endometriosis and OE samples, as well as stromal cells derived from the endometrium of patients with and without endometriosis and OE samples (endometrial stromal cells with endometriosis [ESCs] and cyst-derived stromal cells [CSCs]). The effects of an NLRP3 inhibitor (MCC950) on ESCs and CSCs survival and IL-1ß production were evaluated. We then administered MCC950 to a murine model of OE to evaluate its effects on OE lesions and ovarian function. RESULTS: NLRP3 gene and protein expression levels were higher in OE and CSCs than in EM and ESCs, respectively. MCC950 treatment significantly reduced the survival of CSCs, but not that of ESCs. Moreover, MCC950 treatment reduced the co-localization of NLRP3 and IL-1ß in CSCs, as well as IL-1ß concentrations in CSCs supernatants. In the murine model, MCC950 treatment reduced OE lesion size compared to phosphate-buffered saline treatment (89 ± 15 vs. 49 ± 9.3 mm3 per ovary; P < 0.05). In the MCC950-treated group, IL-1ß and Ki67 levels in the OE-associated epithelia were reduced along with the oxidative stress markers of granulosa cells. CONCLUSIONS: These results indicated that NLRP3/IL-1ß is involved in the pathogenesis of endometriosis and that NLRP3 inhibitors may be useful for suppressing OE and improving the function of ovaries with endometriosis.

Gasless laparoendoscopic single-site surgery for management of unruptured tubal pregnancy in a woman with moderate COVID-19 pneumonia after administration of remdesivir and casirivimab-imdevimab: A case report.

BACKGROUND: Diagnostic and therapeutic challenges may arise in the management of gynecologic emergencies, such as ectopic pregnancy, for women with severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) infection. CASE: A 33-year-old woman (gravida 3, para 2) with a history of SARS-CoV-2 infection 8 months prior experienced sudden onset of fever and cough. Four days later, she consulted her gynecologist because of a positive pregnancy test and was further referred because of suspected ectopic pregnancy at 11 weeks of gestation, as calculated from her last irregular menstrual period. At triage, the patient complained of dyspnea, chest pain, and cough. Real-time reverse transcription-polymerase chain reaction assay detected SARS-CoV-2, which was subsequently identified to be an L452R variant. Chest computerized tomography (CT) showed moderate COVID-19 pneumonia. Transvaginal ultrasonography and pelvic CT showed a right tubal mass without an intrauterine gestational sac, suggesting right tubal pregnancy. Systemic methotrexate (MTX) therapy was chosen for management of the tubal pregnancy because of the patient's unruptured hemodynamically stable status, along with immediate administration of remdesivir and casirivimab-imdevimab to prevent worsening of the pneumonia. After failed MTX therapy, gasless laparoendoscopic single-site right salpingectomy was performed due to concern for tubal rupture. Four days after surgery, the patient was discharged from the hospital without subsequent complications. CONCLUSIONS: Laparoscopic surgery, preceded by anti-viral therapy for COVID-19, is a feasible option for the management of hemodynamically stable tubal pregnancy in a woman with moderate COVID-19 pneumonia.

Thermotriggered Domino-like Single-Crystal-to-Single-Crystal Phase Transition from Face-to-Edge to Face-to-Face Packing of Anthracenes.

Stimuli-triggered crystal-to-crystal and single-crystal-to-single-crystal (SCSC) transformations have received significant attention in the scientific community. To visualize such phenomenon, controlling the optical properties and the thermodynamic stability of the molecular crystals is a very important research subject. In this report, the selective growth of photoluminescent (PL) 1,8-bisphenylanthracene polymorphic (cI and cII) and 1,2-dichloroethane-inclusion crystals (iC) under various optimized conditions is described. These crystals exhibited unique mechano- and thermoresponsive disordering, crystal-to-crystal phase transition, and SCSC phase transition. In particular, rapid thermostimulus SCSC occurred from blue-PL cI into greenish-blue-PL cII. Interestingly, the SCSC phase transition of cI into cII was triggered by thermal stimuli and propagated spontaneously. Thermotriggered domino-like SCSC phase transition was observed on a fully visible timescale (ca. 125 µm min-1 ).

Polymer Optical Microcavity Sensor for Volatile Organic Compounds with Distinct Selectivity toward Aromatic Hydrocarbons.

A whispering-gallery mode (WGM) optical resonance sensor for volatile organic compounds (VOCs) is developed from polystyrene (PS) microspheres doped with fluorescent ß-cyano-appended oligo(p-phenylenevinylene) (ß-COPV). The ß-COPV-doped PS microspheres (MSCOPV) are formed by the miniemulsion method in a binary solvent. MSCOPV expand upon permeation of VOCs into the PS matrix and exhibit a spectral shift of the WGM resonance peak. The permeation efficiency is highly dependent on the chemical affinity between the analyte and the polymer matrix, with exceptionally high selectivity toward aromatic hydrocarbons such as benzene, toluene, and xylenes (BTXs). The high selectivity and sensitivity of MSCOPV are in clear contrast to those of conventional WGM sensors that just detect VOCs nonpreferentially through adsorption onto the surface.

Lysosomal nitric oxide determines transition from autophagy to ferroptosis after exposure to plasma-activated Ringer's lactate.

Non-thermal plasma (NTP), an engineered technology to generate reactive species, induces ferroptosis and/or apoptosis specifically in various-type cancer cells. NTP-activated Ringer's lactate (PAL) is another modality for cancer therapy at preclinical stage. Here we found that PAL induces selective ferroptosis of malignant mesothelioma (MM) cells, where non-targeted metabolome screening identified upregulated citrulline-nitric oxide (.NO) cycle as a PAL target. .NO probe detected biphasic peaks transiently at PAL exposure with time-dependent increase, which was responsible for inducible . NO synthase (iNOS) overexpression through NF-κB activation. .NO and lipid peroxidation occupied lysosomes as a major compartment with increased TFEB expression. Not only ferrostatin-1 but inhibitors for . NO and/or iNOS could suppress this ferroptosis. PAL-induced ferroptosis accompanied autophagic process in the early phase, as demonstrated by an increase in essential amino acids, LC3B-II, p62 and LAMP1, transforming into the later phase with boosted lipid peroxidation. Therefore, .NO-mediated lysosomal impairment is central in PAL-induced ferroptosis.

Carcinogenesis as Side Effects of Iron and Oxygen Utilization: From the Unveiled Truth toward Ultimate Bioengineering.

Evolution from the first life on earth to humans took ~3.8 billion years. During the time there have been countless struggles among the species. Mycobacterium tuberculosis was the last major uncontrollable species against the human public health worldwide. After the victory with antibiotics, cancer has become the leading cause of death since 1981 in Japan. Considering that life inevitably depends on ceaseless electron transfers through iron and oxygen, we believe that carcinogenesis is intrinsically unavoidable side effects of using iron and oxygen. Many animal models unequivocally revealed that excess iron is a risk for carcinogenesis. This is supported by a variety of human epidemiological data on cancer risk and prognosis. Cancer is basically a disease of the genome with persistently activated oncogenes and inactivated tumor suppressor genes through which iron addiction with ferroptosis-resistance is maintained. Engineering has made a great advance in the past 50 years. In particular, nanotechnology is distinct in that the size of the engineered molecules is similar to that of our biomolecules. While some nano-molecules are found carcinogenic, there are principles to avoid such carcinogenicity with a smart possibility to use nano-molecules to specifically kill cancer cells. Non-thermal plasma is another modality to fight against cancer.

Novel ovarian endometriosis model causes infertility via iron-mediated oxidative stress in mice.

Ovarian endometriosis (OE) provides women of reproductive age with not only severe menstrual pain but also infertility and an increased risk for ovarian carcinogenesis. Whereas peritoneal endometriosis models have been developed with syngeneic implantation of minced uterine tissue and oncogenic K-ras allele with conditional Pten deletion within ovarian surface epithelium generated preneoplastic endometrial glandular morphology, followed by endometrioid adenocarcinoma, there has been no mouse model of OE similar to human counterparts, applicable to preclinical studies. Here we for the first time established a murine OE model that reveals infertility, and evaluated the involvement of iron catalyzed oxidative stress in the pathogenesis. Minced uterine tissue from female mice was implanted on ovarian surface of syngeneic mice after bursectomy to induce OE. Ectopic growth of endometrium was observed in association with ovary 4 weeks after implantation in 85.7% (12/14) of the operated mice with our protocol. Endometriotic lesions involved intestine, pancreas and peritoneal wall. Fibrosis around the ovary was prominent and increased time-dependently in the OE group. Iron accumulation was significantly increased in the OE group, leading to oxidative stress in each stage of the follicles as evaluated by 4-hydroxy-2-nonenal-modified proteins and 8-hydroxy-2'-deoxyguanosine. Expression of follicle stimulating hormone receptor in the follicles revealed a significant decrease during pre-antral, antral and pre-ovulatory phases in the OE group. Finally, the number of pups was significantly reduced in the OE group in comparison to the controls. This model affords an opportunity to evaluate agents or procedures to counteract ovarian endometriosis in the preclinical settings.