Palladium-catalyzed disilylation of ortho-halophenylethylenes enabled by 2-pyridone ligand.

A palladium-catalyzed disilylation reaction applicable for a variety of non-, α-, or ß-substituted and α,ß-disubstituted ortho-halophenylethylenes has been developed. This reaction proceeds with high yields and very low catalyst loadings. The two C-Si bonds of the disilylated products could be well-differentiated chemoselectively in the reaction with various electrophiles.

Congenital dysplasia involving both medial and inferior recti: clinical features and surgical outcomes.

AIM: To investigate the clinical features and surgical outcomes of congenital dysplasia involving both inferior recti (IR) and medial recti (MR) muscles. METHODS: A retrospective review was conducted including cases of simultaneous congenital dysplasia of IR and MR that were diagnosed and surgically treated at the Zhongshan Ophthalmic Center, Sun Yat-sen University, China, from July 2009 to November 2019. Ocular motility, ocular alignment at distance (6 m) and near (33 cm) by prism alternating cover test and stereoacuity were assessed in all patients before and after surgery. RESULTS: A total of five patients (four males and one female; three with right eye and two with left eye congenital dysplasia) were included in this review. The patients ranged in age from 10 to 42y (21±13.4y). The main clinical findings were hypertropia and exotropia of the affected eye, along with motility limitations in adduction and depression. Lateral rectus (LR) recession/transposition combined with IR resection was performed in one case. Two scheduled surgeries were performed in four cases, with one involving superior rectus recession and IR resection and the others LR recession and MR resection. Mean±SD pre-surgical exotropia of 51.0±31.11 prism diopter (PD) and hypertropia of 29.20±7.12 PD in the primary position were decreased to 3.6±12.90 and 3.2±10.09 PD, respectively, at two years after surgery, with a success rate of 60% and an under-correction rate of 40%. CONCLUSION: The main clinical features associated with simultaneous MR/IR congenital dysplasia are hypertropia and exotropia of the affected eye along with motility limitations in adduction and depression. Scheduled two-stage surgeries achieved a success rate of 60%.

Congenital ocular counter-roll: a review of cases treated exclusively by ophthalmologists.

AIM: To review the demographics, clinical manifestations, and surgical experiences of patients with congenital ocular counter-roll, whose treatments were performed exclusively by ophthalmologists. METHODS: A retrospective review was conducted consisting of patients who received strabismus surgery between 2017 to 2019. Patients with obvious ocular counter-roll were included. RESULTS: A total of 7008 patients who received strabismus surgery, 28 (12 males, 16 females) were diagnosed as congenital ocular counter-roll, accounting for 0.40%. All patients were initially misdiagnosed: 21 patients were misdiagnosed as superior oblique palsy (SOP), 3 as inferior oblique overaction, 2 as dissociated vertical deviation (DVD), 1 as superior oblique overaction with A-pattern exotropia, and 1 as medial rectus palsy. The mean±SD age was 12.4±9.4y (range 2.5-36y). The most common clinical findings included ocular counter-roll, vertical deviation or vertical deviation combined with outward deviation and head tilt. At follow-up, an excellent surgical result was achieved in 20 patients. Preoperative horizontal deviation of 26±24 prism diopter (PD) and vertical deviation of 18±12 PD were reduced to 0±12 PD (P=0.0001) and 3±4 PD (P=0.001), respectively. CONCLUSION: Congenital ocular counter-roll is a rare supranuclear vertical strabismus caused by congenital abnormalities involving vestibule-ocular reflex pathways. In addition to ocular counter-roll, the most salient clinical features included, but are not limited to, hyperdeviation, outward deviation, overelevation in adduction and head tilt.

Palladium-catalyzed allene synthesis enabled by ß-hydrogen elimination from sp2-carbon.

The rational design based on a deep understanding of the present reaction mechanism is an important, viable approach to discover new organic transformations. ß-Hydrogen elimination from palladium complexes is a fundamental reaction in palladium catalysis. Normally, the eliminated ß-hydrogen has to be attached to a sp3-carbon. We envision that the hydrogen elimination from sp2-carbon is possible by using thoroughly designed reaction systems, which may offer a new strategy for the preparation of allenes. Here, we describe a palladium-catalyzed cross-coupling of 2,2-diarylvinyl bromides and diazo compounds, where a ß-vinylic hydrogen elimination from allylic palladium intermediate is proposed to be the key step. Both aryl diazo carbonyl compounds and N-tosylhydrazones are competent carbene precursors in this reaction. The reaction mechanism is explored by control experiments, KIE studies and DFT calculations.

Di-(2-ethylhexyl) phthalate induces testicular endoplasmic reticulum stress and germ cell apoptosis in adolescent mice.

Di-(2-ethylhexyl) phthalate (DEHP) is a male reproductive toxicant. This research is aimed at investigating the effect of pubertal DEHP exposure on testicular endoplasmic reticulum (ER) stress and germ cell apoptosis. Five-week-old male mice were orally administered with DEHP (0, 0.5, 50, or 500 mg/kg/day) for 35 days. Testis weight and sperm count were reduced in mice exposed to 500 mg/kg/day DEHP. The number of seminiferous tubules in stages VII-VIII, mature seminiferous tubules, was reduced and the number of seminiferous tubules in stages IX-XII, immature seminiferous tubules, was elevated in mice treated with 500 mg/kg/day DEHP. Numerous apoptotic germ cells were observed in mouse seminiferous tubules exposed to 50 and 500 mg/kg/day DEHP. Moreover, cleaved caspase-3 was elevated in mouse testes exposed to 500 mg/kg/day DEHP. In addition, Bcl-2 was reduced and Bax/Bcl-2 was elevated in mouse testes exposed to 500 mg/kg/day DEHP. Additional experiment showed that GRP78, an ER molecular chaperone, was downregulated in mouse testes exposed to 500 mg/kg/day DEHP. Testicular p-IRE-1α, p-JNK, and CHOP, three markers of ER stress, were upregulated in mice exposed to 500 mg/kg/day DEHP. These results suggest that pubertal exposure to high doses of DEHP induces germ cell apoptosis partially through initiating ER stress in testes.

Stereoselective synthesis of conjugated trienes via 1,4-palladium migration/Heck sequence.

Conjugated trienes are ubiquitous structures in natural products and organic functional molecules. An efficient 1,4-palladium migration/Heck sequence was developed for the highly stereoselective synthesis of trisubstituent 1,3,5-trienes, which were found to undergo easy E/Z isomerization in the presence of light.

Corneal graft melting: a systematic review.

Corneal graft melting is a severe complication of keratoplasty. This review is to summarize the incidence, the pathogenesis, the risk factors, the prognosis and the prevention of corneal graft melting after keratoplasty. We systematically searched PubMed, Web of Science and WanFang database to retrieve potentially eligible articles about relevant clinical reports and animal experiments. We read the full texts to identify eligible articles. The selection of studies and data extraction were performed independently by two reviewers. In conclusion, the pathogenesis of corneal graft melting is complicated, and many risk factors are closely related to corneal graft melting. Analysis of pathogenesis and risk factors of corneal graft melting can facilitate the development of targeted therapies to better guide clinical practice.

Long-term 1-nitropyrene exposure induces endoplasmic reticulum stress and inhibits steroidogenesis in mice testes.

1-Nitropyrene (1-NP) is a representative nitro-polycyclic aromatic hydrocarbon from diesel exhaust. Recently, we found that maternal 1-NP exposure caused fetal growth retardation and disturbed cognitive development in adolescent female offspring. To investigate long-term 1-NP exposure on spermatogenesis and steroidogenesis, male mice were exposed to 1-NP (1.0 mg/kg/day) by gavage for 70 days. There was no significant difference on relative testicular weight, number of testicular apoptotic cells and epididymal sperm count between 1-NP-exposed mice and controls. Although long-term 1-NP exposure did not influence number of Leydig cells, steroidogenic genes and enzymes, including STAR, P450scc, P45017α and 17ß-HD, were downregulated in 1-NP-expoed mouse testes. Correspondingly, serum and testicular testosterone (T) levels were reduced in 1-NP-exposed mice. Additional experiment showed that testicular GRP78 mRNA and protein were upregulated by 1-NP. Testicular phospho-IRE1α and sliced xbp-1 mRNA, a downstream molecule of IRE1α, were elevated in 1-NP-exposed mice. Testicular phospho-PERK and phospho-eIF2α, a downstream molecule of PERK pathway, were increased in 1-NP-exposed mice. Testicular NOX4, a subunit of NAPDH oxidase, and HO-1, MDA, two oxidative stress markers, were increased in 1-NP-exposed mice. Testicular GSH and GSH/GSSG were decreased in 1-NP-exposed mice. These results suggest that long-term 1-NP exposure induces reactive oxygen species-evoked ER stress and disrupts steroidogenesis in mouse testes.

Sequential Cross-Coupling/Annulation of ortho-Vinyl Bromobenzenes with Aromatic Bromides for the Synthesis of Polycyclic Aromatic Compounds.

A sequential cross-coupling/annulation of ortho-vinyl bromobenzenes with aromatic bromides was realized, providing a direct and modular approach to access polycyclic aromatic compounds. A vinyl-coordinated palladacycle was proposed as the key intermediate for this sequential process. Excellent chemoselectivity and regioselectivity were observed in this transformation. The practicability of this method is highlighted by its broad substrate scope, excellent functional group tolerance, and rich transformations associated with the obtained products.

Synthesis, Structure and Spectroscopy Study of a 1D Copper Coordination Polymer Based on a Carboxybenzyl Viologen Ligand and SCN-Anion.

A zwitterionic viologen derivative ligand, 1,1'-bis(4-carboxybenzyl)-4 4'-bipyridinium dichloride (H2BpybcCl2) as a multifunctional ligand, has been synthesized incorporating a 4,4'-bipyridine core with two carboxylate groups as a. building block, specifically designed for the rational construction of metal-organic frameworks. H2BpybcCl2 ligand is a multifunctional ligand that contains viologen's specific functions and carboxylate coordination groups. The coordination polymers of viologen carboxylate with copper thiocyanate are not reported to date. A novel copper coordination polymer, [Cu(SCN)2 (Bpybc)] (I) was by solution diffusion method and characterized by single-crystal X-ray diffraction, XRD, elemental analyses, IR spectroscopy, UV-Vis DRS, TG analysis and liquid-state luminescent properties. Compound I crystallized in the monoclinic system with C2/c space group. Crystal data for complex I is as follow: a=19. 508(4) A, b=9. 474(2) Å, c =16. 963(3) Å, α=90°, ß=124. 92(3)°, γ=90°. Two SCN-anions were coordinated to the Cu2+ cation forming a [Cu(SCN)2] unit. Complex I was built up by [Cu(SCN)2] units bridged sequentially by ladder-shaped Bpybc ligands to form one-dimensional zigzag chains running along the [203] direction. The chains were held together by π-π interaction between the pyridine rings and phenyl rings, thus yielding a 3-D extended supramolecular network. The UV-Visible absorption spectra show the absorption bands of π-π* transitions of Bpybc ligands and d-->d transition of Cu2+. The liquid-state luminescent property of compound I was investigated at room temperature. Attractively, the complex exhibits strong blue emission peak at 533 nm (λEx=360 nn) that can be assigned to intraligand transition of Bpybc ligand when it was excited at 360 nm.

Nonradiative recombination--critical in choosing quantum well number for InGaN/GaN light-emitting diodes.

In this work, InGaN/GaN light-emitting diodes (LEDs) possessing varied quantum well (QW) numbers were systematically investigated both numerically and experimentally. The numerical computations show that with the increased QW number, a reduced electron leakage can be achieved and hence the efficiency droop can be reduced when a constant Shockley-Read-Hall (SRH) nonradiative recombination lifetime is used for all the samples. However, the experimental results indicate that, though the efficiency droop is suppressed, the LED optical power is first improved and then degraded with the increasing QW number. The analysis of the measured external quantum efficiency (EQE) with the increasing current revealed that an increasingly dominant SRH nonradiative recombination is induced with more epitaxial QWs, which can be related to the defect generation due to the strain relaxation, especially when the effective thickness exceeds the critical thickness. These observations were further supported by the carrier lifetime measurement using a pico-second time-resolved photoluminescence (TRPL) system, which allowed for a revised numerical modeling with the different SRH lifetimes considered. This work provides useful guidelines on choosing the critical QW number when designing LED structures.

Enhanced 5-fluorouracil cytotoxicity in high COX-2 expressing hepatocellular carcinoma cells by wogonin via the PI3K/Akt pathway.

Combination therapies may increase the antitumor effects and reduce the adverse effects for the treatment of hepatocellular carcinoma. In this study, we determined the effects of 5-fluorouracil alone or in combination with wogonin in vitro and in vivo, and we investigated the possible mechanisms. The combination of these 2 drugs led to a decrease in survival and a significant synergistic inhibitory effect on high COX-2 expression in SMMC-7721 hepatocellular carcinoma (HCC) cells. Furthermore, the results show that this combination inhibits COX-2 expression and increases sensitivity to chemotherapeutic agents partly through regulating the PI3K/Akt signaling pathway. Moreover, the combination treatment caused a significant growth inhibition of human tumor xenografts in vivo. In conclusion, wogonin may increase the cytotoxicity of some antineoplastic agents and it can be used in combination with these agents as a novel therapeutic regimen for HCC treatment.

Oroxylin A improves the sensitivity of HT-29 human colon cancer cells to 5-FU through modulation of the COX-2 signaling pathway.

5-Fluorouracil (5-FU) is a principal drug for the treatment of colorectal cancer. Due to its low response and high toxicity, synergistic effects of 5-FU in combination with other drugs have been widely researched. This study investigated whether oroxylin A improved the sensitivity of HT-29 human colon cancer cells to 5-FU. A correlation between COX-2 inhibition by oroxylin A and a synergistic effect of 5-FU on the growth of HT-29 cells was observed, and a COX-2 pathway for this effect was recognized; oroxylin A evidently elevated the level of reactive oxygen species in HT-29 cells, which subsequently inhibited COX-2 expression and enhanced the susceptibility of HT-29 cells to 5-FU. Likely also related to COX-2 inhibition, oroxylin A decreased PGE(2) levels in HT-29 cells. The synergistic effect of 5-FU induced by oroxylin A was also found in the suppression of Bcl-2 and in the activation of P53, Bax, PARP, and procaspase-3 proteins in HT-29 cells. Ultimately, a combination of 5-FU with oroxylin A significantly reduced the growth of HT-29 tumors in nude mice compared with treatment with 5-FU or oroxylin A alone. In conclusion, a combination of 5-FU and oroxylin A has a significant synergistic effect in the inhibition of HT-29 cell proliferation in vitro and controls HT-29 tumor growth in vivo. This synergistic effect may be mainly related to COX-2 inhibition by oroxylin A in HT-29 cells.