[Successful polatuzumab vedotin and rituximab therapy for post-CAR-T relapse of diffuse large B-cell lymphoma].

Relapse or progressive disease after chimeric antigen receptor T-cell (CAR-T) treatment remains a major issue for poor-risk aggressive large B-cell lymphoma. However, limited data are available on post-CAR-T use of polatuzumab vedotin. Here we describe the case of a patient with diffuse large B-cell lymphoma (DLBCL) who experienced relapse three months after CD19-directed CAR-T therapy with tisagenlecleucel. However, the relapsed lesions rapidly disappeared following treatment with polatuzumab vedotin and rituximab. Notably, long-term remission was achieved without severe cytopenia, infections or peripheral neuropathy, showing the therapeutic benefit of polatuzumab vedotin for CAR-T failure.

Proton Chelating Ligands Drive Improved Chemical Separations for Rhodium.

Current methods for the extraction of rhodium carry the highest carbon footprint and worst pollution metrics of all of the elements used in modern technological applications. Improving upon existing methods is made difficult by the limited understanding of the molecular-level chemistry occurring in extraction processes, particularly in the hydrometallurgical separation step. While many of the precious metals can be separated by solvent extraction, there currently exist no commercial extractants for Rh. This is due to its complicated mixed speciation upon leaching into hydrochloric acid, which gives rise to difficulties in designing effective reagents for solvent extraction. Herein we show that the diamidoamine reagent N- n-hexylbis( N-methyl- N- n-octylethylamide)amine transports Rh(III) from aqueous HCl into an organic phase as the monoaquated dianion [RhCl5(H2O)]2- through the formation of an outer-sphere assembly; this assembly has been characterized by experimentation (slope analysis, FT-IR and NMR spectroscopy, EXAFS, SANS, and ESI-MS) and computational modeling. The paper demonstrates the importance of applying a broad range of techniques to obtain a convincing mode of action for the complex processes involved in anion recognition in the solution phase. A consistent and comprehensive understanding of how the ligand operates to achieve Rh(III) selectivity over the competitor anion Cl- has emerged. This knowledge will guide the design of extractants and thus offers promise for improving the sustainability of metal extraction from both traditional mining sources and the recycling of secondary source materials.

Solid-state one-way photoisomerisation of Z,E,Z-1,6-(4,4'-diphenyl)hexa-1,3,5-triene dicarboxylate examined using higher-order derivative spectra and powder XRD patterns.

Higher order derivative spectra were applied at first to one-way ZEZ-to-EEE photoisomerisation of dimethyl ester (ZEZ-DPH1) of the titled compound in a methylcyclohexane solution. Many common crossing points emerged in UV-induced derivative-spectral changes to reveal the direct ZEZ-to-EEE photoisomerisation without the transient formation of an intermediate to suggest the bicycle-pedal mechanism. The solid-state photoisomerisation was subsequently monitored by tracing changes in the fourth-order derivatives of absorption spectra of a thin crystalline layer of ZEZ-DPH1 prepared by the drop-casting method, because the distortion of absorption spectra due to light scattering is cancelled. It was suggested that the solid-state photochemical event consists of three steps: fast ZEZ-to-EEE photoisomerisation, a subsequent slow ZEZ-to-EEE photoisomerisation and very slow disappearance of the EEE-isomer. Studies on powder XRD were also carried out for a drop-cast solid layer of ZEZ-DPH1 to disclose the coexistence of a crystal form other than the original one, and the former exhibited faster ZEZ-to-EEE photoisomerisation when compared with the original crystal form. The results revealed by XRD analysis are in line with those obtained by higher-order derivative spectra, confirming the solid-state one-way photoisomerisation to take place through the bicycle-pedal process.

[Primary breast diffuse large B-cell lymphoma developing subsequent to estramustine therapy for prostate cancer].

An 85-year-old male presented with 1-year history of a right breast mass. Needle biopsy of the mass revealed diffuse proliferation of large lymphoid cells that were positive for CD20, BCL2, BCL6, and MUM1 and negative for CD5, CD10, MYC, and EBER. The patient was diagnosed as having diffuse large B-cell lymphoma, a type of primary breast lymphoma (PBL). Sex hormone imbalance, which causes conditions such as gynecomastia, is associated with PBL development in males. Estramustine is a nitrogen mustard moiety linked to estradiol. For 5 years, the patient underwent estramustine therapy for treating prostate cancer. Our case suggests an important role of estrogen in PBL development.

Correction: Effects of p-substituents on electrochemical CO oxidation by Rh porphyrin-based catalysts.

Correction for 'Effects of p-substituents on electrochemical CO oxidation by Rh porphyrin-based catalysts' by Shin-ichi Yamazaki et al., Phys. Chem. Chem. Phys., 2010, 12, 8968-8976.

Efficient asymmetric hydrogenation of α-acetamidocinnamates through a simple, readily available monodentate chiral H-phosphinate.

An air-stable, simple (R(P))-mentylbenzylphosphinate, readily available in large quantities, can efficiently induce the rhodium-catalyzed asymmetric hydrogenation of α-acetamidocinnamates with high enantioselectivity (up to 99.6% ee). Intramolecular hydrogen bonding plays an important role in this asymmetric induction.

Fluorescence properties of (E,E,E)-1,6-di(n-naphthyl)-1,3,5-hexatriene (n = 1, 2): effects of internal rotation.

The fluorescence spectroscopic properties of (E,E,E)-1,6-di(n-naphthyl)-1,3,5-hexatrienes (1, n = 1; 2, n = 2) have been investigated in solution and in the solid state. In solution, the absorption maxima (λ(a)) of the lowest-energy band (1, 374 nm; 2, 376 nm in methylcyclohexane) were similar for 1 and 2, whereas the fluorescence maxima (λ(f)) (1, 545 nm; 2, 453 nm) and quantum yields (φ(f)) (1, 0.046; 2, 0.68) were very different regardless of the solvent polarity. The fluorescence spectrum of 1 was independent of the excitation wavelength (λ(ex)), whereas the spectrum of 2 was weakly λ(ex)-dependent. In the solid state, the spectroscopic properties of 1 and 2 were similar (λ(a) = 437-438 nm, λ(f) = 496-505 nm, φ(f) = 0.04-0.07). The origins of emission are both considered to be mainly monomeric. With the help of single-crystal X-ray structure analysis and ab initio quantum chemical calculation, we conclude that the red-shifted and weak emission of 1 in solution originates from a planar excited state having small charge transfer character, reached from a twisted Franck-Condon state by the excited-state geometrical relaxation accompanied by the internal rotation around the naphthalene (Ar)-CH single bond. The similar fluorescence properties of 1 and 2 in the solid state can be attributed to the restriction of the geometrical relaxation. The effects of the Ar-CH rotational isomerism on the fluorescence properties in solution, for 2 in particular, are also discussed.

Mogamulizumab for post-transplant relapse of adult T-cell leukemia/lymphoma: a case study.

Mogamulizumab (MOG), a humanized monoclonal anti-CCR4 antibody, exerts strong antibody-dependent cellular cytotoxic effects on CCR4-positive adult T-cell leukemia/lymphoma (ATLL) cells. As CCR4 is highly expressed on regulatory T cells as well as ATLL cells, pre-transplant MOG induces severe graft-versus-host disease (GvHD). However, limited data are available on post-transplant use of MOG for relapsed ATLL. Here we describe the case of a patient with ATLL who experienced post-transplant relapse with involvement of peripheral blood, skin, lungs, and lymph nodes. Neither tacrolimus dose reduction nor cytotoxic chemotherapy was effective, but a single dose of MOG (1 mg/kg) induced complete remission. After treatment with MOG, leukemic cells in the peripheral blood rapidly disappeared, and the skin, lymph node, and lung lesions gradually regressed. Most notably, the long-term remission was accompanied by recurrence of moderate acute GvHD (grade II, skin stage 2, gut stage 1, liver stage 0). Our findings indicate that MOG can augment allogeneic immune-mediated anti-tumor reactions through graft-versus-ATLL (GvATLL) even during post-transplant relapse involving the lymph nodes and lungs, along with inducing GvHD.

Temporally regulated asymmetric neurogenesis causes left-right difference in the zebrafish habenular structures.

The habenular neurons on both sides of the zebrafish diencephalon show an asymmetric (laterotopic) axonal projection pattern into the interpeduncular nucleus. We previously revealed that the habenula could be subdivided into medial and lateral subnuclei, and a prominent left-right difference in the size ratio of these subnuclei accounts for the asymmetry in its neural connectivity. In the present study, birth date analysis showed that neural precursors for the lateral subnuclei were born at earlier stages than those for the medial subnuclei. More neurons for the early-born lateral subnuclei were generated on the left side, while more neurons for the late-born medial subnuclei were generated on the right side. Genetic hyperactivation and repression of Notch signaling revealed that differential timing determines both specificity and asymmetry in the neurogenesis of neural precursors for the habenular subnuclei.

Highly selective 1,4- and 1,6-addition of P(O)-H compounds to p-quinones: a divergent method for the synthesis of C- and O-phosphoryl hydroquinone derivatives.

The reaction of P(O)-H compounds with p-quinones could proceed through either 1,4- or 1,6-addition pathways by employing different additives to selectively give the corresponding C- and O-phosphoryl hydroquinone derivatives in good yields. Oxidative double 1,4-addition of P(O)-H compounds to p-quinones was also achieved by tuning the solvent, affording a facile synthesis of bis-substituted hydroquinones with phosphorus functionality. Further studies on these reactions by using optically active H-phosphinates showed that all addition reactions took place stereospecifically with retention of configuration at the phosphorus center. The findings lead to the establishment of a divergent method for the synthesis of C- and O-phosphoryl hydroquinone derivatives from easily available P(O)-H compounds.

The 3-year cumulative survival rates of posterior monolithic zirconia crowns and their antagonist teeth, and their influencing factors.

PURPOSE: The purpose of this study was to evaluate the 3-year cumulative survival rates of posterior single monolithic zirconia crowns (MZCs) and their antagonists, and to analyze the influencing factors. METHODS: The clinical outcomes of posterior single MZCs and their abutment teeth with antagonists, and the antagonists between April 2014 and September 2020 were evaluated retrospectively. The 3-year cumulative survival rates were calculated and associations between the survival time and predictor variables ("Jaw", "Tooth", and "Pulpal condition") were also verified using Cox proportional hazards models and hazard ratios (HRs). RESULTS: The 3-year cumulative survival rate of single MZCs was 89.8% (9 of 177 MZCs, 95% confidence interval (CI): 80.0-95.1%). Cox proportional hazards models showed non-vital teeth were significantly associated with failure (HR: 2.76e + 9, P = 0.012). The 3-year cumulative survival rate of antagonists was 94.8% (7 of 171 antagonists, 95% CI: 89.3-97.6%). Non-vital antagonists were also identified as an independent predictor for failure in Cox proportional hazards models (HR: 7.83, P = 0.03). CONCLUSION: Although posterior single MZCs were clinically acceptable, non-vital pulpal condition could be a potential risk factor for failures in the abutment and antagonist teeth of MZCs.

Probiotic Effects of a Marine Purple Non-Sulfur Bacterium, Rhodovulum sulfidophilum KKMI01, on Kuruma Shrimp (Marsupenaeus japonicus).

Purple non-sulfur bacteria (PNSB) are used as probiotics in shrimp aquaculture; however, no studies have examined the probiotic effects of PNSB in shrimp at the gene expression level. In this study, we examined the effects of a marine PNSB, Rhodovulum sulfidophilum KKMI01, on the gene expression of kuruma shrimp (Marsupenaeus japonicus). Short-term (3 days) effects of R. sulfidophilum KKMI01 on the gene expression in shrimp were examined using small-scale laboratory aquaria experiments, while long-term (145 days) effects of R. sulfidophilum KKMI01 on the growth performance and gene expression were examined using 200-ton outdoor aquaria experiments. Gene expression levels were examined using qRT-PCR. Results of the short-term experiments showed the upregulation of several molting-related genes, including cuticle proteins, calcification proteins, and cuticle pigment protein, suggesting that PNSB stimulated the growth of shrimp. The upregulation of several immune genes, such as prophenoloxidase, antimicrobial peptides, and superoxide dismutase, was also observed. In the 145-day outdoor experiments, the average body weight at harvest time, survival rate, and feed conversion ratio were significantly improved in PNSB-treated shrimp, and upregulation of molting and immune-related genes were also observed. When PNSB cells were added to the rearing water, the effective dosage of PNSB was as low as 103 cfu/mL, which was more than a million times dilution of the original PNSB culture (2-3 × 109 cfu/mL), indicating that R. sulfidophilum KKMI01 provides a feasible and cost-effective application as a probiotic candidate in shrimp aquaculture.

Effects of Seed Bio-Priming by Purple Non-Sulfur Bacteria (PNSB) on the Root Development of Rice.

The effects of seed bio-priming (seed soaking) with purple non-sulfur bacteria (PNSB) on the grain productivity and root development of rice were examined by a field study and laboratory experiments, respectively. Two PNSB strains, Rhodopseudomonas sp. Tsuru2 and Rhodobacter sp. Tsuru3, isolated from the paddy field of the study site were used for seed bio-priming. For seed bio-priming in the field study, the rice seeds were soaked for 1 day in water containing a 1 × 105 colony forming unit (cfu)/mL of PNSB cells, and the rice grain productivities at the harvest time were 420, 462 and 504 kg/are for the control, strain Tsuru2-primed, and strain Tsuru3-primed seeds, respectively. The effects of seed priming on the root development were examined with cell pot cultivation experiments for 2 weeks. The total root length, root surface area, number of tips and forks were evaluated with WinRhizo, an image analysis system, and strains Tsuru2- and Tsuru3-primed seeds showed better root development than the control seeds. The effects of seed priming with the dead (killed) PNSB cells were also examined, and the seed priming with the dead cells was also effective, indicating that the effects were attributed to some cellular components. We expected the lipopolysaccharide (LPS) of PNSB as the effective component of PNSB and found that seed priming with LPS of Rhodobacter sphaeroides NBRC 12203 (type culture) at the concentrations of 5 ng/mL and 50 ng/mL enhanced the root development.

Facile regio- and stereoselective hydrometalation of alkynes with a combination of carboxylic acids and group 10 transition metal complexes: selective hydrogenation of alkynes with formic acid.

A facile, highly stereo- and regioselective hydrometalation of alkynes generating alkenylmetal complex is disclosed for the first time from a reaction of alkyne, carboxylic acid, and a zerovalent group 10 transition metal complex M(PEt(3))(4) (M = Ni, Pd, Pt). A mechanistic study showed that the hydrometalation does not proceed via the reaction of alkyne with a hydridometal generated by the protonation of a carboxylic acid with Pt(PEt(3))(4), but proceeds via a reaction of an alkyne coordinate metal complex with the acid. This finding clarifies the long proposed reaction mechanism that operates via the generation of an alkenylpalladium intermediate and subsequent transformation of this complex in a variety of reactions catalyzed by a combination of Brϕnsted acid and Pd(0) complex. This finding also leads to the disclosure of an unprecedented reduction of alkynes with formic acid that can selectively produce cis-, trans-alkenes and alkanes by slightly tuning the conditions.

Post-transplant food anaphylaxis in an adult cord blood transplant recipient (Ms. No. IJHM-D-20-01037R1).

Transplant acquired food allergy (TAFA) is a well-known complication following pediatric liver transplantation, but post-cord blood transplantation (post-CBT) TAFA has rarely been reported. Here, we describe a case of new-onset food anaphylaxis after CBT in an adult patient that demonstrates that post-CBT allergen-challenge is not a risk for long-term allergic sensitization even in adult recipients. The patient was a 39-year-old Japanese man with aggressive NK cell leukemia. He had no previous history of allergies. After receiving CBT, the patient had an unbalanced diet with high preference for bread, bananas, miso-soup, cow's milk, cheese, egg, sesame and buckwheat soba noodles, and experienced repeated diarrhea. Six months later, he developed symptoms such as vomiting, epigastric pain, diarrhea, high fever and hypotension. The condition was initially diagnosed as enterocolitis, but symptoms recurred after consumption of buckwheat. Anaphylaxis induced by buckwheat was confirmed with serum radioallergosorbent tests (RAST), showing allergen-specific IgE for buckwheat (greater than 100 U/mL, Class 6) and egg ovomucoid (Class 4). Nineteen months after a buckwheat and egg-free diet, serum RAST for buckwheat and egg significantly improved. As a result, the patient acquired a tolerance and was able to consume buckwheat and egg without allergic symptoms.

Stereospecific coupling of H-phosphinates and secondary phosphine oxides with amines and alcohols: a general method for the preparation of optically active organophosphorus acid derivatives.

The reaction of H-phosphinates and secondary phosphine oxides with amines and alcohols proceeds highly stereospecifically to give the corresponding coupling products with inversion of configuration at the phosphorus center under the Atherton-Todd reaction conditions. This finding leads to the establishment of a general and efficient method for the synthesis of a variety of optically active organophosphorus acid derivatives from the easily available chiral H-phosphinates and secondary phosphine oxides.

Stereospecific halogenation of P(O)-H bonds with copper(II) chloride affording optically active Z1Z2P(O)Cl.

A general and efficient method for the preparation of optically active Z1Z2P(O)Cl from the easily prepared optically active H-phosphinates and H-phosphine oxides was reported. H-Phosphinates and H-phosphine oxides react stereospecifically with CuCl2 to produce the corresponding optically active Z1Z2P(O)Cl with retention of configuration at the phosphorus center. Optically active Z1Z2P(O)Cl reacts easily with a variety of nucleophiles to produce other chiral organophosphorus acid derivatives with inversion of configuration at phosphorus.

Effects of p-substituents on electrochemical CO oxidation by Rh porphyrin-based catalysts.

Electrochemical CO oxidation by several carbon-supported rhodium tetraphenylporphyrins with systematically varied meso-substituents was investigated. A quantitative analysis revealed that the p-substituents on the meso-phenyl groups significantly affected CO oxidation activity. The electrocatalytic reaction was characterized in detail based on the spectroscopic and X-ray structural results as well as electrochemical analyses. The difference in the activity among Rh porphyrins is discussed in terms of the properties of p-substituents along with a proposed reaction mechanism. Rhodium tetrakis(4-carboxyphenyl)porphyrin (Rh(TCPP)), which exhibited the highest activity among the porphyrins tested, oxidized CO at a high rate at much lower potentials (<0.1 V vs. a reversible hydrogen electrode, at 60 degrees C) than the present PtRu catalysts. This means that CO is electrochemically oxidized by this catalyst when a slight overpotential is applied during the operation of a proton exchange membrane fuel cell. This catalyst exhibited little H(2) oxidation activity, in contrast to Pt-based catalysts.

Fluorescence spectroscopic properties of nitro-substituted diphenylpolyenes: effects of intramolecular planarization and intermolecular interactions in crystals.

The steady-state absorption and fluorescence properties of (E,E,E)-1,6-diaryl-1,3,5-hexatrienes (2, aryl = 2-nitrophenyl; 3, aryl = 3-nitrophenyl; 4, aryl = 4-nitrophenyl) have been investigated in solution and in the crystalline state. The solid-state absorption spectra of 2-4 shifted to longer wavelengths than those in solution. A combination of theoretical calculations and single-crystal X-ray structure analyses shows considerable planarization of molecules in the solid state, which is mainly responsible for the spectral red shifts. The effects of intermolecular interactions on the absorption spectra appeared to be relatively small in these crystals. This is consistent with the monomeric origin of the solid-state emission. Molecule 2 was nonfluorescent in all solvents studied, probably due to the efficient nonradiative deactivation from ionic species produced by excited-state intramolecular proton transfer (ESIPT) along the C-H...O-type hydrogen bonds. The fluorescence of 3, observed only in medium polar solvents, originated from an intramolecular charge transfer (ICT*) state, while that of 4 derived from locally excited (LE*) and/or ICT* states depending on the solvent polarity. All three molecules exhibited LE* fluorescence in the solid state. No observation of ICT* emission in crystals strongly suggests the twisted geometries for ICT* (TICT) of 3 and 4 in solution. The measurable fluorescence from crystal 2 can be attributed to the restricted torsional motions in the solid excited state.

(Z,E,Z)-1,6-Di-1-naphthyl-hexa-1,3,5-triene.

The title compound, C(26)H(20), lies about an inversion centre. The naphthalene unit and the hexa-triene chain are each approximately planar (maximum deviations of 0.0143 and 0.0042 Å, respectively), and are inclined to one another at a dihedral angle of 49.20 (4)°. The dihedral angle between the two naphthalene ring systems of neighboring mol-ecules is 85.71 (4)°.