Phosphoric Acid-Catalyzed Alkene Difunctionalization of 2-Vinylpyridines via HOMO/LUMO Biactivated Diels-Alder Reaction.

The difunctionalization of vinylpyridines based on the cyclization strategy remains rare and underdeveloped, in contrast to the well-developed hydrogen functionalization. Current exploration on [4 + 2] cyclization of vinylpyridines mainly relies on extremely high temperatures and the LUMO activation of vinylpyridines using boron trifluoride as a strong Lewis acid. Herein, we established a phosphoric acid-catalyzed [4 + 2] cyclization reaction of 3-vinyl-1H-indoles and 2-vinylpyridines by means of the LUMO/HOMO bifunctional activation model. This protocol features mild reaction conditions, high functional group tolerance, broad substrate compatibility, and high diastereoselectivity, enabling the efficient construction of various functionalized pyridine-substituted tetrahydrocarbazoles with prominent potential in drug discovery.

The Addition of an Ultra-Small Amount of Black Phosphorous Quantum Dots Endow Self-Healing Polyurethane with a Biomimetic Intelligent Response.

This study explores new applications of black phosphorus quantum dots (BPQDs) by adding them to self-healing material systems for the first time. Self-healing polyurethane with an ultra-small amount of BPQDs has biomimetic intelligent responsiveness and achieves balance between its mechanical and self-healing properties. By adding 0.0001 wt% BPQDs to self-healing polyurethane, the fracture strength of the material increases from 3.0 to 12.3 MPa, and the elongation at break also increases from 750% to 860%. Meanwhile, the self-healing efficiency remains at 98%. The addition of BPQDs significantly improves the deformation recovery ability of the composite materials and transforms the surface of self-healing polyurethane from hydrophilic to hydrophobic, making it suitable for applications in fields such as electronic skin and flexible wearable devices. This study provides a simple and feasible strategy for endowing self-healing materials with biomimetic intelligent responsiveness using a small amount of BPQDs.

LncRNA SNHG16 promotes colorectal cancer cell proliferation, migration, and epithelial-mesenchymal transition through miR-124-3p/MCP-1.

Colorectal cancer (CRC) has been the third leading cause of cancer-associated deaths. LncRNA SNHG16 is reported to be involved in metastasis of CRC cells. However, the mechanism by which SNHG16 regulates CRC progression is poorly understood. The proliferation of CRC cells was examined by MTT. Wound healing and transwell assay were used to measure migration and invasion ability. RT-qPCR and western blot were used to examine gene expression. Immunofluorescence was conducted to evaluate the EMT of CRC cells. Luciferase reporter assay were used to confirm direct interaction between miR-124-3p and SNHG16 or MCP-1. The interaction between miR-124-3p and SNHG16 was detected by RIP and RNA pull down assay. H&E staining was used to test the histomorphological changes of hepatic metastatic nodules. Finally, xenograft tumor experiment was utilized to determine tumor growth in vivo. SNHG16 and miR-124-3p were dysregulated in human colorectal tumors or cells. Knockdown of SNHG16 led to attenuate cell proliferation, migration, invasion, and EMT of CRC cells. And xenograft tumor experiment showed that SNHG16 might influence tumor growth. In contrast, miR-124-3p exerted the antitumor effects. Knockdown of miR-124-3p can reverse the effect of sh-SNHG16 on CRC cells. miR-124-3p could directly bind to SNHG16 or MCP-1. More importantly, MCP-1 acts as a critical effector mediating the role of SNHG16/ miR-124-3p in CRC cells. In summary, our data suggest that SNHG16 plays a contributory role in proliferation, migration, and EMT of CRC cells via miR-124-3p/MCP-1 axis, which offers a rationale for targeting SNHG16 and developing therapeutic drugs to treat CRC.

QTL mapping of the genetic basis of stem diameter in soybean.

MAIN CONCLUSION: QTL mapping of stem diameter was carried out in three RIL populations using a high-density genetic map, and candidate genes related to stem diameter were predicted. Stem diameter is an important agronomic trait affecting soybean lodging and productivity. However, this trait is underexploited, and the underlying genetic mechanism in soybean remains unclear. In this study, three recombinant inbred line (RIL) populations, including 156 F10 lines from Nannong 94-156 × Bogao (N × B), 127 F9 lines from Dongnong 50 × Williams 82 (D × W), and 146 F9 lines from Suinong 14 × Enrei (S × E), were used to identify QTLs for soybean stem diameter across multiple environments. Phenotype analysis revealed that stem diameter exhibited strong positive correlations with plant height and 100-seed weight, two of the most important yield components. A total of 12 QTLs for stem diameter were identified on eight chromosomes across three RIL populations and five environments. The most influential QTL that was stably identified across all the populations and environments, q11, explained 12.58-26.63% of the phenotypic variation. Detection of several environment-specific QTLs, including q14, q16, and q20, suggests that environments may also have important effects in shaping the natural variation in soybean stem diameter. Furthermore, we predicted candidate genes underlying the QTLs and found that several promising candidate genes may be responsible for the variation in stem diameter in soybean. Overall, the markers/genes linked closely or underlying the major QTLs may be used for marker-assisted selection of soybean varieties to enhance lodging resistance and even yield. Our results lay the foundation for the fine mapping of stem development-related genes to reveal the molecular mechanisms.

Photoinduced Acetylation of Anilines under Aqueous and Catalyst-Free Conditions.

A green and efficient visible-light induced functionalization of anilines under mild conditions has been reported. Utilizing nontoxic, cost-effective, and water-soluble diacetyl as photosensitizer and acetylating reagent, and water as the solvent, a variety of anilines were converted into the corresponding aryl ketones, iodides, and bromides. With advantages of environmentally friendly conditions, simple operation, broad substrate scope, and functional group tolerance, this reaction represents a valuable method in organic synthesis.

Photoinduced Deaminative Coupling of Alkylpyridium Salts with Terminal Arylalkynes.

A novel and simple Z-alkene synthesis by the photocatalyzed coupling reactions of alkylpyridium salts, which were prepared from primary amines, with terminal aryl alkynes at room temperature is reported here. A wide range of primary amines, which contain different functional groups, were tolerated under these conditions. The mild reaction conditions, broad substrate scope, functional group tolerance, and operational simplicity make this deaminative coupling reaction a valuable method in organic syntheses.

Solvent Effects: Syntheses of 3,3-Difluorooxindoles and 3-Fluorooxindoles from Hydrazonoindolin-2-one by Selectfluor.

Efficient syntheses of 3,3-difluorooxindoles and 3-fluorooxindoles via fluorination of hydrazonoindolin-2-one with Selectfluor are reported. Under different solvent conditions, this method produced 3,3-difluorooxindoles and 3-fluorooxindoles selectively. The broad substrate scope and mild reaction conditions make this transformation a valuable method in drug discovery and development.

High expression of Golgi phosphoprotein-3 is associated with poor survival in patients with hepatocellular carcinoma.

Golgi phosphoprotein 3 (GOLPH3) is recently demonstrated to function as an oncogene involved in the development and progression of cancers. However, little is known about GOLPH3 expression and its clinical significance in hepatocellular carcinoma (HCC). The levels of GOLPH3 messenger RNA (mRNA) and protein in HCC cell lines and fresh tissues were determined by quantitative RT-PCR and western blotting. Additionally, the protein expression of GOLPH3 was detected in 167 paraffin-embedded HCC samples by immunohistochemistry. GOLPH3 mRNA and protein was overexpressed in HCC cell lines and tissues than the immortalized normal hepatocyte cell line LO2 and the adjacent nontumorous live tissues, respectively. High GOLPH3 expression was positively correlated with high serum AFP level (P = 0.015) and more tumor recurrence or metastasis (P = 0.010). In addition, HCC patients with high GOLPH3 expression had poorer overall survival (hazard ratio (HR), 1.87; 95 % confidence interval (CI), 1.19-2.94; P = 0.006) and poorer disease-free survival (HR, 1.90; 95 % CI, 1.21-2.98; P = 0.005) than those with low GOLPH3 expression. The cumulative 5-year survival rate was only 35.19 % (95 % CI, 26.18-44.20 %) in the high GOLPH3 expression group, whereas it was 55.93 % (95 % CI, 43.26-68.60 %) in the low GOLPH3 expression group. Furthermore, multivariate Cox regression analysis demonstrated that the expression of GOLPH3, tumor size, and tumor multiplicity were independent prognostic predictors for HCC patients. GOLPH3 was overexpressed in HCC at both the mRNA and protein levels, and high expression of GOLPH3 could be served as a novel and potential prognostic biomarker for HCC patients.

Reconstruction of the medial patellofemoral ligament using hamstring tendon graft with different methods: a biomechanical study.

OBJECTIVE: To measure the tensile strength of the normal medial patellofemoral ligament (MPFL), and evaluate the biomechanics of different fixation methods of the hamstring tendon graft on the patella. METHODS: Eight fresh cadaver knees were prepared by isolating the patella, leaving only the MPFL as its attachment to the medial condyle of femur. The MPFL was reconstructed by three different methods: four-suture fixation, anchors-single suture fixation, and anchors-double suture fixation. The tensile strength and the elongation of the normal MPFL and the tendon grafts were measured. RESULTS: The tensile strength of the four-suture fixation group (234.86±49.02 N) was stronger than that of the normal MPFL (146.91±25.30 N, P=0.0014) and the anchors-single suture group (159.17±49.07 N, P=0.0077), while weaker than that of the anchors-double suture group (314.74±78.46 N, P=0.0052) CONCLUSIONS: With regard to the tensile strength, the four-suture fixation method is reliable for clinical use. Compared with the anchor-suture method, the four-suture fixation method which has no specific implants is more economical, convenient and efficient.

Transcriptome Analysis of Antrodia cinnamomea Mycelia from Different Wood Substrates.

Antrodia cinnamomea, an edible and medicinal fungus with significant economic value and application prospects, is rich in terpenoids, benzenoids, lignans, polysaccharides, and benzoquinone, succinic and maleic derivatives. In this study, the transcriptome of A. cinnamomea cultured on the wood substrates of Cinnamomum glanduliferum (YZM), C. camphora (XZM), and C. kanehirae (NZM) was sequenced using the high-throughput sequencing technology Illumina HiSeq 2000, and the data were assembled by de novo strategy to obtain 78,729 Unigenes with an N50 of 4,463 bp. Compared with public databases, about 11,435, 6,947, and 5,994 Unigenes were annotated to the Non-Redundant (NR), Gene Ontology (GO), and Kyoto Encyclopedia of Genes and Genome (KEGG), respectively. The comprehensive analysis of the mycelium terpene biosynthesis-related genes in A. cinnamomea revealed that the expression of acetyl-CoA acetyltransferase (AACT), acyl-CoA dehydrogenase (MCAD), 3-hydroxy-3-methylglutaryl-coenzyme A (HMG-CoA), mevalonate pyrophosphate decarboxylase (MVD), and isopentenyl diphosphate isomerase (IDI) was significantly higher on NZM compared to the other two wood substrates. Similarly, the expression of geranylgeranyltransferase (GGT) was significantly higher on YZM compared to NZM and XZM, and the expression of farnesyl transferase (FTase) was significantly higher on XZM. Furthermore, the expressions of 2,3-oxidized squalene cyclase (OCS), squalene synthase (SQS), and squalene epoxidase (SE) were significantly higher on NZM. Overall, this study provides a potential approach to explore the molecular regulation mechanism of terpenoid biosynthesis in A. cinnamomea.

[Distinguish reasons for the variety of intraoperative transcranial magnetic motor evoked potential: the anaesthesia or the operative injury].

OBJECTIVE: To find a way to discriminate operative reason from anaesthesia reason for the changes of intraoperative transcranial magnetic motor evoked potentials (MEPs). METHODS: In 26 patients under Etomidate/Fentanyl anesthesia from February 2001 to June 2004, MEPs elicited by transcranial magnetic stimulation were recorded from tibialis anterior muscles, simultaneously bispectral index (BIS) and train-of-four stimulation (TOF) were used to monitor the anesthesia depth and neuromuscular blockade respectively. MEP, BIS and measurements of TOF at different anesthesia depth and muscular relaxation were recorded synchronously, statistical analysis of this data set was done in order to find the inherent relationship between these variables. RESULTS: Under anesthesia, MEP amplitude was always positively correlated with the corresponding BIS and TOF value. A regression equation could be built, with which the MEP amplitude could be reckoned based on realtime BIS and T(1)/T(c). In case of spinal cord injury, the measured amplitude value would significantly deviate from predicted one, which suggested that the change of MEP was because of the operation, but not the anaesthesia or neuromuscular blockade. Each patient had his or her own regression equation, which was different from each other. CONCLUSIONS: The establishment of regression equation from MEPs, BIS and TOF is very useful to distinguish reasons of the changes of transcranial magnetic MEPs during surgery, and with this technique, the intraoperative MEP monitoring should be more reliable and practicable.

Photo-catalyzed acetoxysulfoximination of styrene with sulfoximidoyl thianthrenium salt.

We report the design and synthesis of a redox-active thianthrenium-containing sulfoximination reagent. Photo-catalyzed acetoxysulfoximination of styrene with various functional groups is described. Preliminary mechanistic studies indicated that the sulfoximination reagent (2aa) received a single electron transfer (SET) from the photo-excited Ir(ppy)3 catalyst to produce a sulfoximidoyl radical as a key intermediate in this transformation.

[Expressions of integrinalpha2beta1 and CD133 in benign prostatic hyperplasia complicated by prostatitis and their significance].

OBJECTIVE: To study the expressions of Integrinalpha2beta1 and CD133 in benign prostatic hyperplasia (BPH) complicated by prostatitis and their significance. METHODS: Specimens were obtained from 56 BPH patients undergoing transvesical prostatectomy. Paraffin sections of the specimens were subjected to HE staining for pathological examination of inflammatory changes under the light microscope. Twenty-four patients with simple BPH were included in Group A, and the other 32 with BPH complicated with prostatitis in Group B. The expressions of Integrinalpha2beta1 and CD133 in the prostatic tissues of the two groups were determined by immunohistochemistry, Western blotting and IPP6.0 image analysis software. RESULTS: The expressions of Integrinalpha2beta1 and CD133 were significantly higher in Group B than in A (P < 0.05), and so were the mean relative value of the optical density of Integrinalpha2beta1 (0.29 +/- 0.18 vs 0.04 +/- 0.03) and that of CD133 (0.08 +/- 0.07 vs 0.0020 +/- 0.0018) (P < 0.05). CONCLUSION: Inflammation can up-regulate the expressions of Integrinalpha2beta1 and CD133 in BPH tissue.

[Prostate cancer with five different histological features: a case report and review of the literature].

OBJECTIVE: To study the clinical manifestations, pathological characteristics and treatment methods of prostate cancer with five different histological features. METHODS: We reported 1 case of prostate cancer with five different histological features and further analyzed the diagnosis, pathology and treatment of the disease by reviewing the relevant literature. RESULTS: The patient was an 84-year-old male, admitted due to difficult urination and dribbling urine for 1 year, hematuria for 8 months and deterioration for 2 weeks. Prostate cancer was indicated by rectal examination, ultrasonography, CT, MRI and PSA, and confirmed by biopsy. Considering the general condition of the patient, we performed electrotransurethral resection under epidural anesthesia to alleviate his urinary symptoms and remove suspected tumor tissues. Postoperative pathology showed the case to be prostate adenocarcinoma, histologically characterized by cribriform carcinoma, acinar carcinoma, diffuse invasive carcinoma, ductal carcinoma, and mucinous adenocarcinoma, with a Gleason score of 9. Bicalutamide and goserelin were administered postoperatively. Systemic metastasis occurred 10 months later, and the patient died 1 year after the operation. CONCLUSION: Prostate cancer with five different histological features is extremely rare. Its early diagnosis is difficult and mainly depends on pathological and immunohistochemical examinations, and radical prostatectomy can be considered for its treatment.

[The utility of neuronavigation in the microsurgery for cerebral cavernous malformations].

OBJECTIVE: To evaluate the utility of neuronavigation in the microsurgery for cerebral cavernous malformations. METHODS: In a retrospective study, 47 patients with cavernous malformations were involved from January 1995 to December 2010. Fourteen cases admitted into hospital from January 1995 to December 2002 were treated without neuronavigation (conventional group), the focus localization was based on magnetic resonance imaging (MRI) images, anatomic landmarks, and the experiences of the neurosurgeon. In the other 33 cases admitted after February 2002 to December 2010, surgeries were performed with neuronavigation using the Medtronic Stealth Station TREON or TRIA system (neuronavigation group). Excision of the cavernomas were all performed microsurgically, surrounding gliotic rim and hemosiderin stained tissue were resected in the case of epilepsy, and a few patients underwent extended hippocampal resection or multiple subpial transection. RESULTS: With the use of neuronavigation, the extent of craniotomy reduced from 5.2 cm to 3.6 cm (P < 0.01), and deeper cavernoma focuses could be treated surgically. There were no changes with regard to the mean size of the cavernomas, the mean time of surgery and hospital stay (P > 0.05), but the mean time of anaesthesia was prolonged from 164 min to 197 min (P < 0.01). Cavernomas were resected completely in all 47 cases, which was confirmed by postoperative MRI recheck. The conditions of all patients were improved or remain unchanged, and no significant differences in the clinical outcome could be evaluated between the two groups. CONCLUSIONS: Application of neuronavigation-assisted microsurgery of intracranial cavernous malformations surgery, helps reduce the surgical trauma, and has security and reliability.

[Undifferentiated prostate sarcoma with cartilage metaplasia: a case report and review of the literature].

OBJECTIVE: To investigate the clinical presentations and pathologic features of undifferentiated sarcoma of the prostate with cartilage metaplasia, and to clarify its category. METHODS: We analyzed the clinical data of a case of undifferentiated sarcoma of the prostate with cartilage metaplasia treated by surgical resection. The tumor tissue was subjected to routine HE and immunohistochemical staining, its histological structure and immunohistochemical expression were observed under the light microscope, and relevant literature on its manifestations was reviewed. RESULTS: The case was pathologically diagnosed as gray prostate tumor, with chondrosarcomatous and undifferentiated malignant mesenchymal components under the light microscope. Immunohistochemical staining revealed vimentin (+), local CD117 (+/-), SMA (-), Des (-), myoglobin (-), CD34 (-), CK7 (-), and CK8 (-). Tumor metastasis was found 2 months after the operation, and the patient died 4 months later. CONCLUSION: Undifferentiated sarcoma of the prostate with cartilage metaplasia is a very rare and highly malignant aggressive tumor, which can be diagnosed by biopsy and immunohistochemistry.

[Microsurgical management of tuberculum sellae meningiomas].

OBJECTIVE: To explore the approach and efficacy of microsurgery for tuberculum sellae meningiomas. METHODS: The clinical data of 56 patients with tuberculum sellae meningiomas treated at our department from 1991 - 2009 were analyzed retrospectively. There were 20 males and 36 females with an age range of 32 - 65 years old (mean: 46). All patients underwent microsurgery through pterional, unilateral subfrontal, orbitozygomatic or supraorbital keyhole approach. RESULTS: Among these patients, there were total resection (n = 51) and subtotal resection (n = 5). Postoperatively, 53 patients recovered well, 2 had a mild disability, 1 suffered a severe disability and there was no mortality. CONCLUSION: Most cases of tuberculum sellae meningiomas can be removed safely and totally. Several approaches may be employed to achieve the best outcomes. Microsurgery can markedly boost the total resection rate of tuberculum salle meningiomas and lower the postoperative complications and mortality.

[Microsurgical management of anterior clinoidal meningiomas].

OBJECTIVE: To explore the method and efficacy of microsurgery for anterior clinoidal meningiomas. METHODS: The clinical data of 53 patients with anterior clinoidal meningiomas treated from 1991-2009 were analyzed retrospectively. There were 15 males and 38 females. The age range was 33 - 65.5 years old (mean: 45.5). All patients underwent microsurgery through pterional, extended pterional, frontotemporal, frontotemporal and orbitozygomatic approaches. RESULTS: Of 53 patients, total, subtotal and partial resections were performed in 38, 10 and 5 cases respectively. Postoperatively, 48 patients recovered well, 4 had mild disability, 1 severe disability and no dead case. CONCLUSION: Most anterior clinoidal meningiomas can be removed safely and effectively. Several approaches may be used to achieve the best results. Microsurgical operation can offer a great aid in an effective resection of anterior clinoidal meningiomas and reduce the postoperative complications and mortality. Postoperative radiotherapy should be carried out for the residual tumor invading cavernous sinus or internal carotid artery.