Effective Tools for the Metal-Catalyzed Regiodivergent Direct Arylations of (Hetero)arenes.

The direct functionalization of two different C-H bonds of the same organic molecule using different procedures - also called regiodivergent C-H bond functionalization - currently represents an important research topic in organic chemistry, as it demonstrates the versatility of C-H bond functionalization methodology. Over the last decade, the number of tools to control such regiodivergent C-H bond functionalizations has increased significantly. In this account, we will present the various tools that allowed us to arylate different positions of various (hetero)arenes, via a C-H bond functionalization, using palladium or ruthenium catalysis.

"One-stop shop": safety and efficacy of combining atrial septal defect occlusion and left atrial appendage closure for patients with atrial septal defect and atrial fibrillation.

BACKGROUND: One-stop occlusion, which is defined as the combination of atrial septal defect [ASD] or patent foramen ovale [PFO] occlusion and left atrial appendage [LAA] closure, in patients with ASD/PFO and atrial fibrillation (AF) has not yet been investigated systematically. This study aimed to evaluate the safety and efficacy of one-stop occlusion in the treatment of adult patients with ASD/PFO and AF. METHODS: Inpatients with AF and ASD/PFO were recruited between August 2014 and April 2019. Preoperatively, transthoracic echocardiography (TTE) and transesophageal echocardiography (TEE) were conducted to identify the ASD/PFO size and margin, presence of thrombus in the LAA, and LAA orifice width and depth at 0°, 45°, 90°, and 135°. After confirmation of the indications of LAA closure (LAAC) and ASD/PFO occlusion, the procedures were performed simultaneously under general anesthesia. Oral anticoagulants were administered for 45-60 days, followed with regular evaluation of TTE and TEE. RESULTS: Forty-nine patients (age, 65.6 ± 9.6 years) were recruited in this study, including 24 patients with ASD and 25 patients with PFO. They were treated with LAAC and ASD/PFO occlusion successfully. The mean ASD size and mean diameter of the ASD occluders were 14.2 ± 7.7 and 25.4 ± 8.5 mm, respectively. The mean PFO size was 3.5 ± 0.4 mm. The mean maximal LAA orifice width and depth were 20.5 ± 3.4 and 28.3 ± 3.6 mm, respectively. All patients were implanted with a Watchman device (diameter, 27.1 ± 2.9 mm). Postoperatively, all patients took anticoagulants orally for 45-60 days, and their mean postoperative follow-up duration was 29.0 ± 12.1 months. Postoperative TEE showed that all had normal positioning of the LAA and ASD/PFO occluders. At 45-60 days after operation, TEE showed that the LAA and ASD/PFO occluder were in the normal position; however, two patients who took warfarin and novel oral anticoagulants, respectively, have developed occluder thrombosis. After adjusted anticoagulant therapy, TEE showed that the thrombus disappeared at 6 months after operation. CONCLUSION: One-stop occlusion is safe and effective for the treatment of adult patients with ASD/PFO and AF. It is also feasible to administer warfarin or novel oral anticoagulants after operation.

Regioselective Pd-catalyzed direct C1- and C2-arylations of lilolidine for the access to 5,6-dihydropyrrolo[3,2,1-ij]quinoline derivatives.

The Pd-catalyzed C-H bond functionalization of lilolidine was investigated. The use of a palladium-diphosphine catalyst associated to acetate bases in DMA was found to promote the regioselective arylation at α-position of the nitrogen atom of lilolidine with a wide variety of aryl bromides. From these α-arylated lilolidines, a second arylation at the ß-position gives the access to α,ß-diarylated lilolidines containing two different aryl groups. The one pot access to α,ß-diarylated lilolidines with two identical aryl groups is also possible by using a larger amount of aryl bromide. The synthesis of 5,6-dihydrodibenzo[a,c]pyrido[3,2,1-jk]carbazoles from lilolidine via three successive direct arylations is also described. Therefore, this methodology provides a straightforward access to several lilolidine derivatives from commercially available compounds via one, two or three C-H bond functionalization steps allowing to tune their biological properties.

[Relationship among gingival thickness, underlying alveolar bone thickness, and sagittal root position in the maxillary anterior].

OBJECTIVE: This study aimed to explore the relationship among gingival thickness (GT), underlying alveolar bone thickness (BT), and sagittal root position in the maxillary anterior measured by cone-beam computed tomography (CBCT). The theoretical foundation was applied to aesthetic dentistry, implant treatment planning, and therapeutic effect assessment. METHODS: A total of 40 young volunteers with healthy periodontal status were involved in this research [16 males and 24 females aged 23-34 years with a mean age of (26.30±2.29) years]. Three records were measured by CBCT. GT was measured at the cemento-enamel junction level. Buccal BT was measured at three locations: 1, 3, and 5 mm below the alveolar crest, along the sagittal angle between the long axis of teeth, and along the long axis of the respective alveolar bone. RESULTS: The average GT and alveolar BT thicknesses were (1.08±0.34) mm and (0.79±0.29) mm, respectively. The average angle between teeth and alveolar bone was 18.01°±8.96°. BT was positively associated with GT (r=0.293, P=0.001). The BT of canine was positively associated with the angle between teeth and alveolar bone (r=0.457, P=0.003). CONCLUSIONS: BT was relatively thin. An angle was found between the long axis of teeth and that of the alveolar bone. BT was positively associated with GT. An accurate diagnosis of GT, underlying alveolar BT, and sagittal root position in the maxillary anterior is necessary before implant surgery to devise an appropriate implant treatment plan and achieve a predictable esthetic outcome.

Effects of alveolar ridge preservation on delayed implant osseointegration.

To evaluate the effects of alveolar ridge preservation with Bio-Oss bone substitute (Geistlich Pharma) on delayed implant osseointegration. The 3rd and 4th left and right mandibular premolars were extracted from four adult healthy male and female dogs. For the experimental group, we randomly selected two extraction sockets in each dog to be filled with Bio-Oss bone substitute (Geistlich Pharma). The two remaining extraction sockets remained untreated and served as the control group. Three months after Bio-Oss placement, dental implants were inserted into the alveolar bone of the experimental group and the control group. The osteogenic activity of the bone around the implants was assessed by evaluating the histological morphology and by estimating histomorphometric parameters at 3 and 6 months after delayed implantation. At 3 months, Goldner's trichrome staining analysis showed that the bone-implant contact rate and mineralised bone area around the implant were significantly higher in the experimental group (75.98% ± 8.97% and 69.52% ± 9.63%, respectively) than in the control group (56.13% ± 8.18% and 52.82% ± 7.25%, respectively; P < 0.05). However, at 6 months, the two groups showed no significant difference. Fluorescence microscopy analysis revealed that the average mineralisation apposition rate of the bone tissue around the dental implant in the experimental group at 3 and 6 months was 6.80 ± 0.43 µm and 8.38 ± 0.84 µm, respectively, which was significantly higher than the rate in the control group (P < 0.05). These data indicated that alveolar ridge preservation by using Bio-Oss placement can promote osseointegration of delayed implantation. This may be a promising option for clinical use.

[Application of attached gingiva reconstruction in implant-supported dental prosthesis].

PURPOSE: To explore a method of attached gingiva reconstruction around dental implants and to evaluate its clinical outcomes and technical characters. METHODS: From January 2011 to August 2011, a total of 10 implants were included in this study from 8 patients who had inadequate attached gingiva and needed to undergo secondary operation. A modified apically positioned flap technique was applied to reconstruct attached gingiva at the time of secondary operation. Crown restoration was finished 4 weeks after the operation and the patients were recalled 6 months after restoration. Effective keratinized mucosal width was recorded separately before the operation, 4 weeks after the operation and 6 months after restoration. Clinical examination was conducted 6 months after restoration including modified plaque index(mPI), probing depth(PD), bleeding index(BI) and percentage of bleeding on probing. Statistical analysis was performed using Wilcoxon signed rank test with SPSS18.0 software package. RESULTS: Four weeks after the operation, there was an average increase of 2.41 mm in effective keratinized mucosal width compared with the preoperative value (P<0.05). After 6 months of function, the newly formed keratinized mucosa remained stable and attached to the crown tightly without obvious inflammation. The mean width was (2.64±0.53) mm. Clinical examinations showed a mean mPI of 0.70±0.82, a mean PD of (1.80±0.36) mm, and a mean BI of 0.73±0.64. In terms of bleeding on probing, 23.3% of sites showed positive outcome. CONCLUSIONS: By using the modified apically positioned flap technique at the time of secondary operation, the attached gingiva around implants can be effectively reconstructed. The short-term effects are satisfactory.

Preparation of protamine cationic nanobubbles and experimental study of their physical properties and in vivo contrast enhancement.

In this study, we aimed to prepare a novel type of microbubble (MB), protamine cationic nanobubble (NB), to provide a new vector for tumor gene therapy. We prepared cationic NBs with protamine and other lipid components using mechanical oscillation. The protamine cationic NBs had a mean diameter of 521.2 ± 37.57 nm, a zeta potential of +18.5 mV, and a gene-carrying capacity of 15.69 µg androgen receptor (AR) siRNA per 10(8) NBs. The cationic NBs exhibited superior contrast enhancement for in vivo imaging compared with SonoVue (Bracco, Geneva, Switzerland), and their physical properties did not change significantly after 1 wk; meanwhile, the transfection efficiency of the cationic NBs in androgen-independent prostate cancer cells mediated by ultrasound irradiation was better than that of liposomes (82.17 ± 7.4% vs. 55.04 ± 5.4%, p < 0.01). Therefore, the protamine cationic NB can be considered for use as a novel type of gene-loading MB for ultrasound imaging and MB-mediated gene therapy of tumors.

[Squamous cell papilloma in interdental papilla: a case report].

Squamous cell papilloma is a kind of benign tumor from mucosa stratified squamous epithelium, which usually occurs in cheek, palate, lip and tongue. In this paper, a case of squamous cell papilloma occurred in interdental papilla was reported, and its pathogenesis, clinic features and treatment were discussed.

[A clinical evaluation of the implant denture in the anterior maxilla over 5 years].

PURPOSE: To evaluate the clinical results of implant denture in the anterior maxilla over 5 years. METHODS: From January 2002 to December 2006, two hundred and thirty-four patients with 354 dental implants were followed up for 7-62 months. The results were evaluated by X-ray, clinical examination and patient satisfaction investigation. The 5 year cumulative survival rate (life- table analysis), bone resorption around implants (ANOVA), outcome of soft tissues and esthetics were analyzed using SPSS13.0 software package. RESULTS: The cumulative survival rate was 97.9%; there was no significant difference among different ways of operation (P=1.00); no significant difference in mean crestal bone loss was found among different years (P=0.88); 19.8% gingival papilla achieved Jemt grade 3; 91.7% patients were satisfied with the restoration. CONCLUSIONS: Implantation is an effective method for patients losing upper anterior teeth. The cumulative survival rate is as high as 97.9%.

[Three-dimensional finite element analyses of bone surface stress of two kinds of conjunction implant].

OBJECTIVE: To establish a three-dimension finite element model of mandible with two kinds of dental implant and to study the stress of implant-bone interface. METHODS: Measuring the data of the components of the dental implant and using spiral CT image reconstruction technique to scan the cross section of the mandible. Three-dimension finite element analysis software Unigraphics and MSC. Marc/Mentat were used to build the conjunction model and bone model of two implant systems. Loading 200 N axially and 100 N 30 degrees obliquely on the models respectively, the stress distribution patterns of the bone interface of two implant systems were analyzed. RESULTS: The stress distribution on the bone interface of two implant systems was similar. The peak stress of oblique loading was higher than that of axial loading. The peak stress district of the bone was concentrated on the stricture of the implant cervix, which was more obviously displayed on the Replace Select implant. The peak stresses on the bone interface of Replace Select implant were higher than that of Replace implant in all loadings. CONCLUSION: To Replace Select especially, oblique force should be avoided in clinical practice in case of the bone absorption.

[A study of 202 periodontitis subjects in Chengdu].

OBJECTIVE: To study the severity of periodontitis and risk factors in Chengdu. METHODS: 202 periodontitis patients (65 male, 137 female), aged from 25 to 60, were requested to fill a questionnaire. Probing depth (PD), clinical attachment level (CAL), gingival recession and bleeding on probing (BOP) on 6 sites of each tooth were measured and recorded. RESULTS: The mean PD, AL, gingival recession and BOP% of 202 subjects was (3.2 +/- 0.31) mm, (3.5 +/- 0.37) mm, (0.3 +/- 0.02) mm and 21.16%. 59% of subjects missed at least one tooth. 129 subjects suffered with initial to moderate periodontitis. 73 subject suffered with advanced periodontitis. 40, 86, 55 and 21 subjects had received college education, high school education, middle school education and primary school education. 18% of subjects had smoking history, 67% subjects had tea/coffee history, 66% of subjects had psychosocial problem, and only 8% of subjects had received regular periodontal treatment. There is no relationship between the severity of periodontitis and education. CONCLUSION: It is very important to develop an education program on oral healthy for people in Chengdu.

[Investigation on the association of interleukin-1 genotype polymorphism with chronic periodontitis].

OBJECTIVE: To examine the distribution of IL-1 genotypes among the people with Han nationality of different periodontal health status and to evaluate if there is an association between the genotype of IL-1 and the severity of periodontitis. METHODS: 271 subjects of Han nationality were selected, among them there were 182 cases of chronic periodontitis and 89 subjects of periodontal healthy control. Full periodontal examinations were taken including full-mouth clinical attachment loss measurements, probing depths and bleeding on probing. DNA samples were obtained with buccal swabbing technique and were further analyzed for IL-1 genotype polymorphisms using PCR-RFLP-based method. RESULTS: The results showed a significant increase in the frequency of IL-1A-889/Nco I allele 2, IL-1B + 3953/Taq I allele 2, IL-1B-511/Ava I allele 2, IL-1A-889 plus IL-1B-511 allele 2 and IL-1B + 3953 plus IL-1B-511 allele 2 in patients with severe chronic periodontitis as compared with periodontally healthy controls. CONCLUSION: Findings from this study bring into question the usefulness of the genotypes of allele 2 of IL-1A-889, IL-1B-511 and IL-1B + 3953 as a method for determining the susceptibility of Chinese patients to chronic periodontitis. There is a possible role of IL-1 gene polymorphisms in the susceptibility to chronic periodontitis for some patients.

[The experimental study of facial nerve regeneration through E-PTFE tube with nervous homogenates].

PURPOSE: To investigate the effect of using e-PTFE containing nervous homogenates to repair the rabbit facial nerve defect. METHODS: Thirty-six adult New-Zealand rabbits weighing 2000-2500 g were randomly selected. The right sides were selected as e-PTFE containing nervous homogenates group, 8 mm defect of facial never were made, then the defect was bridged with e-PTFE tube, and the nervous homogenates were implanted into the e-PTFE tube. The left sides were selected as e-PTFE group, 8 mm defect of facial never were made, the proximal and distal stumps were simply bridged with e-PTFE tube. Regeneration of the nerve was assessed by gross observation, nerve electrophysiological test and optical microscope observation. RESULTS: The electrophysiological examination showed that in the e-PTFE group, there was no muscular contraction; while in the homogenates group, the electric stimulus could get through the nerve defect at 4th week. The nerve conduction velocity of the homogenates group recovered better than that of the e-PTFE group at 8th, 12th week. Optical microscope observation showed that at 4th week, in the e-PTFE group, the proximal and distal nerve stumps denervated widely;while in the homogenates group, all the proximal nerve stumps regenerated through the chamber and reached the distal end. At 8th week, in the e-PTFE group, the regenerating nerve fiber got through the nerve defect, the nerve fibers were sparse and arranged in disorder throughout the tube.In the homogenates group, the tube was filled with regenerating nerve fibers which arranged in order. At 12th week, in the e-PTFE group, the nerve fibers lined up in orders, but there existed the phenomena that the nerve fibers were confused. In the homogenates group, regenerating nerve fibers were mature. CONCLUSIONS: From this experiment, we found that the effect of e-PTFE containing nervous homogenates to repair the facial never was better than that of e-PTFE group.

[The study of the relationship of malodor and microbial composition of interdental and subgingival plaques in periodontitis patients].

OBJECTIVE: The study is to investigate the microbial composition of interdental and subgingival plaques of periodontitis patients with or without malodor, to explore the relationships between periodontitis and oral malodor. METHODS: 20 patients of periodontitis with malodor were chosen from 210 patients of periodontitis, and the clinical parameter of plaque index (PLI), gingival bleeding index (GBI) and probing depth (PD) were measured and compared with the control group which had periodontal disease without malodor. During the experiment, the interdental and subgingival microbial samples in both groups were collected and sent to anaerobic culture for 48 hrs, then the total CFU/ml of each sample were counted, and each type of bacteria was separated and identified. All of the data were analyzed by using the statistical software SPSS 10.0. RESULTS: (1) There were no satistical differences on PLI, GBI, PD between experimental group and control group. (2) The percents of leptospira in both interdental and subgingival plaques of test group were significantly higher than that of the control group (P < 0.01). (3) Either the interdental or in subgingival plaques, the count results of CFU/ml were similar in both groups (P > 0.05). (4) The proportions of malodor producing anaerobic bacteria in interdental gingival plaque, such as P. gingivalis and Veillonelia, were singnificantly different between test group and control group. CONCLUSION: The proportions of VSC's producing anaerobic bacteria in interdental gingival plaque may be play the significant roles in oral malodor. Further studies should be taken to elucidate the relationship between malodor and periodontitis.

[Experimental study on using mGTR and venous autografts to repair facial nerve defects in rabbits].

OBJECTIVE: To observe and compare the effects of using mGTR and venous autografts to repair the defect of facial nerve in rabbits. METHODS: mGTR and venous autografts were performed on three groups of rabbits. Then physical and histological examinations were carried out to get the results of these two repair methods. RESULTS: Both the two methods can induce regeneration of facial nerve. The mGTR is more effective and faster in repairing the nerve defect. Three months after operation, the distance of NCV between bilateral facial nerve in mGTR group was (2.10 +/- 1.2) m/s, (6.80 +/- 1.4) m/s in venous autografts, (2.16 +/- 1.6) m/s in nerve transplantation group. Histologically, the facial nerve fibers were arranged regularly and in continuity in mGTR, the facial nerve fibers were arranged irregularly with marked hyperplasia of connective tissues in venous autografts three months after repair. CONCLUSIONS: The mGTR is more effective than venous autografts in repair of facial nerve.