Vasculitis-like herpes zoster in the course of treatment with tofacitinib in ulcerative colitis: An assessment of local viral distribution by RNA in situ hybridization.

A 67-year-old man had taken the janus kinase (JAK) inhibitor, tofacitinib, for ulcerative colitis. He was referred to our department for a refractory ulcer on his lower leg. We suspected vasculitis and performed skin biopsy. Histopathological examination showed multinucleated giant cells in the epidermis and fibrinoid degeneration of small vessels in the upper dermis. Varicella zoster virus (VZV) DNA was detected by polymerase chain reaction and we diagnosed the patient with atypical vasculitis-like herpes zoster. The patient was treated with oral valacyclovir, but the rash persisted and took 2 months to heal. Immunostaining using anti-VZV antibody was positive mainly in epidermal keratinocytes, but was also observed to be positive in cells in the dermis. We further performed RNA in situ hybridization using a VZV ORF9 mRNA probe and clearly showed that the distribution of VZV mRNA extended into the dermis, including the dermal vessel walls and the eccrine sweat glands as well as the epidermis. The internal administration of JAK inhibitors may induce regional widespread VZV infection including vessels and involved in the formation of prolonged vasculitis-like manifestation. RNA in situ hybridization can be a potent tool for detecting the spread of VZV infection in the skin.

Establishment of an MR1 Presentation Reporter Screening System and Identification of Phenylpropanoid Derivatives as MR1 Ligands.

Mucosal-associated invariant T (MAIT) cells are innate-like T cells that are modulated by ligands presented on MHC class I-related proteins (MR1). These cells have attracted attention as potential drug targets because of their involvement in the initial response to infection and various disorders. Herein, we have established the MR1 presentation reporter assay system employing split-luciferase, which enables the efficient exploration of MR1 ligands. Using our screening system, we identified phenylpropanoid derivatives as MR1 ligands, including coniferyl aldehyde, which have an ability to inhibit the MR1-MAIT cell axis. Further, the structure-activity relationship study of coniferyl aldehyde analogs revealed the key structural features of ligands required for MR1 recognition. These results will contribute to identifying a broad range of endogenous and exogenous MR1 ligands and to developing novel MAIT cell modulators.

Construction of a Bicyclo[2.2.2]octene Skeleton via a Visible-Light-Mediated Radical Cascade Reaction of Amino Acid Derivatives with N-(2-Phenyl)benzoyl Groups.

Bridged polycyclic ring systems constitute the core structures of numerous natural products and biologically active molecules. We found that simple biphenyl substrates derived from amino acids participate in a radical cascade reaction under visible light irradiation in the presence of [Ir{dF(CF3)ppy}2(dtbpy)]PF6 to enable the direct construction of bicyclo[2.2.2]octene structures. Isotopic labeling experiments suggested that intramolecular hydrogen atom transfer is involved in the cascade processes.

Pnictogen-Bridged Diphenyl Sulfones as Photoinduced Pnictogen Bond Forming Emission Motifs.

In this study, pnictogen (Pn)-bridged diphenyl sulfones were synthesized as motifs for photoinduced dynamic rearrangement. The newly synthesized sulfones exhibited dual fluorescence at 298 K. Density functional theory calculations revealed that the longer-wavelength fluorescence was derived from the geometries after structural relaxation through photo-driven pnictogen bond formation between the O atom lone pair of the sulfonyl moiety and the antibonding orbital of the Pn-C bond. This is the first report on emission dynamics driven by pnictogen bond formation upon photoexcitation.

Emission Properties of Eu(III) Complexes Containing Arsine and Phosphine Ligands with Annulated Structures.

In this study, we synthesized Eu3+ complexes containing arsine and phosphine oxides with annulated structures as the antenna ligands. The type of bridging in the annulated structures controlled the energy level of the triplet excited state and the intersystem crossing efficiency, leading to different emission properties. Eu3+ complexes bearing the arsine oxides showed a higher intensity ratio of electric/magnetic dipole transitions and energy-transfer efficiency than the complexes with the corresponding phosphine oxides.

Drastic Enhancement of Photosensitized Energy Transfer Efficiency of a Eu(III) Complex Driven by Arsenic.

In this study, we focused on arsenic as a new potential motif for the ligand design of high-efficiency, luminous lanthanide complexes. A Eu3+ complex bearing triphenylarsine oxide had a photosensitized energy-transfer efficiency 7.9 times higher than that of a Eu3+ complex bearing triphenylphosphine oxide. This is mainly due to the heavy-atom effect of arsenic, which was supported by evaluating the photoluminescence spectra of their corresponding Gd3+ complexes.

Systematic Study on the Catalytic Arsa-Wittig Reaction.

Efficient catalytic arsa-Wittig reactions have been developed by using 1-phenylarsolane as a catalyst. A wide array of aldehydes was converted to the corresponding olefins in high yields with moderate to excellent E stereoselectivity in the presence of a catalytic amount of 1-phenylarsolane. Moreover, density functional theory calculations were carried out to afford insight into the E/Z selectivity.

Dipyridinoarsole: a new class of stable and modifiable heteroatom-bridged bipyridines.

Herein, we report our experimental and computational investigations on a stable and modifiable As-bridged dipyridinoheterole, dipyridinoarsole. Oxidation of the arsenic atom changes the frontier orbital energies and quaternization of nitrogen atoms produces electrochromic materials. Dipyridinoarsole is suitable for practical applications due to its superior stability compared to its phosphole analogues.

Dibenzoarsepins: Planarization of 8π-Electron System in the Lowest Singlet Excited State.

Dibenzo[b,f]arsepins possessing severely distorted cores compared to those of other heteropins were synthesized. These derivatives exhibited dual photoluminescence in the green-to-red region (500-700 nm) and the near-ultraviolet region (<380 nm), which could be attributed to the planarization of the arsepin core in the lowest singlet excited (S1 ) state. The computational approach for the assessment of the aromatic indices revealed that the dibenzoarsepins studied show aromaticity (8π system) in the S1 states in line with Baird's rule. The lone pair electrons of the arsenic atoms play a crucial role in the aromaticity in the S1 states.

As-Heteropentacenes: An Experimental and Computational Study on a Novel Class of Heteroacenes.

Arsenic-containing heteropentacenes were synthesized for the first time; bibenzofuran, benzothienyl benzofuran, and bibenzothiophene were bridged by arsenic atoms. Their structures and properties were experimentally and computationally studied using X-ray crystallography, optical and electronic properties, aromaticity, charge carrier mobility, etc. The present findings on the novel class of heteroacenes will expand functional organic chemistry.

Case of cutaneous phaeohyphomycosis caused by Phaeoacremonium sp. in a renal transplant recipient.

We describe a case of cutaneous phaeohyphomycosis in a 61-year-old man receiving re-dialysis treatment for renal failure of a transplanted kidney. He was immunocompromised with steroid and cyclosporin A at onset of an asymptomatic abscess on his right forearm. The abscess arose at the site of a skin injury approximately 1 year prior. Grayish molds isolated from the lesion were morphologically compatible with Phaeoacremonium sp. but nucleotide sequence data of internal transcribed spacer regions of ribosomal RNA gene, actin and ß-tubulin genes were unlike those of any described species. He was successfully treated with a total of 3 weeks of liposomal amphotericin B, but died of pneumonia approximately 3 months after cure of phaeohyphomycosis.

Influence of different post-core systems on impact stress: a pilot study.

UNLABELLED: This pilot study compared impact strain at the core and root surfaces between two different post-core systems. MATERIALS AND METHODS: The form of a bovine mandibular front tooth was modified to resemble that of a human maxillary incisor as a test specimen. A cast post and core (Metal PC) and composite resin and glass fiber-reinforced epoxy resin post (Fiber-Resin PC) system were tested. Four gauges were affixed to the buccal and lingual surfaces of the core and root. The specimens were then embedded in a metal mold using dental stone. A pendulum-type device with a pyramid-shaped metal impact object with a titanium alloy head was used to provide 2 different shock forces. Maximum distortion was measured and analyzed. RESULTS: Distortion at the core at each measurement point and total amount of distortion with Fiber-Resin PC was significantly greater (p<0.05) than that with Metal PC against both impact forces. On the other hand, distortion at the root at the buccal measurement point with Fiber-Resin PC was significantly less than that with Metal PC against both impact forces. Total distortion was significantly less with Fiber-Resin PC than that with Metal PC against the greater impact shock. Acceleration with Fiber-Resin PC was significantly less than that with Metal PC against both impact forces. CONCLUSION: Fiber-Resin PC has the potential to protect remaining root against traumatic force. This suggests that a Fiber-Resin PC is more suitable for non-vital teeth against not only occlusal but also traumatic impact force.

Chronopharmacological assessment identified GLUT4 as a factor responsible for the circadian variation of the hypoglycemic effect of tolbutamide in rats.

The circadian relationship between the pharmacokinetics and pharmacodynamics of tolbutamide in rats was analyzed using a compartment model. The basal concentration of plasma glucose had a circadian rhythm with the acrophase at 15:19 h. After intravenous administration of tolbutamide at 06:00, 14:00, or 18:00 h, the hypoglycemic effect showed a circadian variation, with the greatest effect at 18:00 h and the lowest effect at 06:00 h. The time courses of unbound tolbutamide concentration in plasma after intravenous administration were predicted using the model-estimated total concentration of tolbutamide and the albumin concentration and resulted in profiles that did not vary with the time of administration. Significant low insulin resistance was observed at 18:00 h to i.v. glucose and insulin loads. There was no obvious time dependency in the expression of glucose transporter 4 (GLUT4) in epididymal adipocytes. The hypoglycemic rate estimated from the plasma glucose concentration was described by the conventional pharmacokinetic-pharmacodynamic model with an effect compartment. The time courses of theoretical signals in the effect compartment described the observed circadian changes in the increased expression profile of GLUT4 normalized by the increased plasma insulin (IRI) concentration (ΔGLUT4/ΔIRI) after dosing. Thus, the time dependency in glucose uptake is responsible for the circadian variation of the hypoglycemic effect of tolbutamide.

Case of remitting seronegative symmetrical synovitis with pitting edema (RS3PE syndrome) showing dermatomyositis-like eruption.

A 73-year-old woman developed linear erythema at the sites of scratching-induced scars on the bilateral thighs 2 weeks before the initial consultation. Subsequently, edematous erythema developed in the upper eyelids, dorsum of the nose and the face, and pitting edema in the dorsum of the bilateral hands and feet. The C-reactive protein (CRP) level was 8.2 mg/dL and erythrocyte sedimentation rate (ESR) 121 mm/h. The antinuclear antibody titer was 1:160, and rheumatoid factor (RF) and anti-Jo-1 antibody were negative. X-ray examination of the bilateral hands showed neither narrowing of the joint spaces nor bone erosion. Ga scintigraphy showed synovitis of the bilateral wrists. A diagnosis of remitting seronegative symmetrical synovitis with pitting edema syndrome (RS3PE) was made. The erythema disappeared after diclofenac sodium administration. However, because the joint swelling and pitting edema did not improve, p.o. administration of prednisolone (20 mg/day) was initiated. The CRP and ESR levels normalized 2 months after the initiation of administration, and pitting edema disappeared after 3 months. We report this case because linear erythema like that observed in dermatomyositis has not been described as eruptions associated with RS3PE.

[A case report of prosthodontic treatment for the influence of occlusal discord on the whole body].

PATIENT: The patient was a 19-year-old man who visited the hospital with chief complaints of headache, stiffness of shoulders, and giddiness. The skull, mandible, and splint, and their relation with cervical vertebra, were considered, and new knowledge was acquired. Since the fulcrum of the movement axis at the time of opening and closing had shifted below the dens, it was diagnosed as TMD. Splint treatment was performed and the main symptoms had improved 3 months later. DISCUSSION: It is thought that the jawbone of the upper and lower sides of class II occlusion had adapted to class III, and would cause various whole-body conditions. CONCLUSION: Although the influence of the posture of cervical vertebra and the whole-body deformation of submaxilla is considered, there are many unknown points and further study is required.

Plasmid-encoded genes specifying aniline oxidation from Acinetobacter sp. strain YAA.

Acinetobacter sp. strain YAA is able to use aniline and o-toluidine as the sole carbon and energy source. This strain has several different plasmids and acridine orange curing suggested that aniline utilization in strain YAA was plasmid-encoded. The gene cluster involved in aniline oxidation was cloned in Escherichia coli JM109 from the total plasmid DNA of strain YAA. A recombinant E. coli containing an 18.5 kb insert fragment showed yellow colouration on aniline-containing plates, indicating the formation of 2-hydroxymuconic semialdehyde from aniline. In addition, subcloning of a 9.0 kb SalI fragment from the insert in E. coli resulted in the accumulation of catechol. Southern hybridization studies indicated that the aniline oxygenase gene (atdA) was present on one of the plasmids, pYA1. These results suggest that in strain YAA aniline is degraded via catechol through a pathway involving meta-cleavage of the benzene-ring by plasmid-encoded genes including atdA.