Chemodivergent Tandem Radical Cyclization of Alkene-Substituted Quinazolinones: Rapid Access to Mono- and Di-Alkylated Ring-Fused Quinazolinones.

Chemodivergent tandem radical cyclization offers exciting possibilities for the synthesis of structurally diverse cyclic compounds. Herein, we revealed a chemodivergent tandem cyclization of alkene-substituted quinazolinones under metal- and base-free conditions, this transformation is initiated by alkyl radicals produced from oxidant-induced α-C(sp3 )-H functionalization of alkyl nitriles or esters. The reaction resulted in the selective synthesis of a series of mono- and di-alkylated ring-fused quinazolinones by modulating the loading of oxidant, reaction temperature, and reaction time. Mechanistic investigations show that the mono-alkylated ring-fused quinazolinones is constructed by the key process of 1,2-hydrogen shift, whereas the di-alkylated ring-fused quinazolinones is mainly achieved through crucial steps of resonance and proton transfer. This protocol is the first example of remote second alkylation on the aromatic ring via α-C(sp3 )-H functionalization and difunctionalization achieved by association of two unsaturated bonds in radical cyclization.

The construction of benzimidazo[2,1-a]isoquinolin-6(5H)-ones from N-methacryloyl-2-phenylbenzoimidazoles through radical strategies.

Benzimidazo[2,1-a]isoquinolin-6(5H)-one constitutes a structurally unique class of tetracyclic N-heterocycles that are found throughout a myriad of biologically active natural products, pharmaceutical compounds, and functional materials. Various synthetic routes for the preparation of benzimidazo[2,1-a]isoquinolin-6(5H)-ones have been reported. In particular, the use of N-methacryloyl-2-phenylbenzoimidazoles to construct benzimidazo[2,1-a]isoquinolin-6(5H)-ones through various radical strategies have attracted widespread attention due to the versatility and simple preparation of raw materials, as well as the step-economy and mild reaction conditions. Using representative examples, we highlight significant progress in the synthesis of benzimidazo[2,1-a]isoquinolin-6(5H)-ones, including the selection of the catalytic system, substrate scope, mechanistic understanding, and applications. The contents of this review focus on the development of C-, S-, P-, and Si-centered radical addition-intramolecular cyclization strategies.

Recent progress in the radical α-C(sp3)-H functionalization of ketones.

The direct use structurally simple ketones as α-ketone radical sources for α-C(sp3)-H functionalization is a sustainable and powerful approach for constructing complex and multifunctional chemical scaffolds with diverse applications. The reactions of α-ketone radicals with alkenes, alkynes, enynes, imides, and imidazo[1,2-a]pyridines have broadened the structural diversity and complexity of ketones. Through chosen illustrative examples, we outline the recent progress in the development of methods that enable the radical α-C(sp3)-H functionalization of ketones, with an emphasis on radical initiation systems and possible mechanisms of the transformations. The application of these strategies is illustrated by the synthesis of several biologically active molecules and drug molecules. Further subdivision is based on substrate type and reaction type.

The clinical effect of trochanteric slide osteotomy combined with a cementless femoral conical stem in total hip replacement for the treatment of Crowe type IV developmental dysplasia of the hip.

BACKGROUND: Total hip replacement (THR) for Crowe type IV developmental dysplasia of the hip (DDH) is still challenging due to specific joint deformities and the high incidence of post-operative complications. OBJECTIVE: This study aimed to evaluate the clinical effect of trochanteric slide osteotomy (TSO) combined with a cementless femoral conical stem in THR for the treatment of Crowe type IV DDH. METHODS: Thirty-one total hip replacements (26 patients) with Crowe type IV DDH were performed using TSO combined with a cementless femoral conical stem. Surgical outcomes were evaluated using leg length discrepancy (LLD), Harris hip score, and post-operative complications. RESULTS: The average pre-operative LLD was 51 mm (range 46-58 mm), decreasing to an average of 10 mm (range 8-12 mm) post-operatively. As a result, the post-operative incidence of the Trendelenburg sign significantly decreased compared with the pre-operative incidence (P< 0.05). Bony union was identified in 26 hips (83.9%), fibrous union in four (12.9%), and non-union in one (3.2%). No acetabular or femoral component loosening, dislocation, or deep infection around the component was found in any of the patients during the follow-up period (27 to 39 months). The average Harris hip score improved from 63.0 ± 3.0 (range 58-69) to 93.3 ± 2.0 (range 91-96). CONCLUSION: TSO combined with a cementless conical stem in THR is an appropriate option for patients with high congenital hip dislocation.

Mapping Chinese annual gross primary productivity with eddy covariance measurements and machine learning.

Annual gross primary productivity (AGPP) is the basis for grain production and terrestrial carbon sequestration. Mapping regional AGPP from site measurements provides methodological support for analysing AGPP spatiotemporal variations thereby ensures regional food security and mitigates climate change. Based on 641 site-year eddy covariance measuring AGPP from China, we built an AGPP mapping scheme based on its formation and selected the optimal mapping way, which was conducted through analysing the predicting performances of divergent mapping tools, variable combinations, and mapping approaches in predicting observed AGPP variations. The reasonability of the selected optimal scheme was confirmed by assessing the consistency between its generating AGPP and previous products in spatiotemporal variations and total amount. Random forest regression tree explained 85 % of observed AGPP variations, outperforming other machine learning algorithms and classical statistical methods. Variable combinations containing climate, soil, and biological factors showed superior performance to other variable combinations. Mapping AGPP through predicting AGPP per leaf area (PAGPP) explained 86 % of AGPP variations, which was superior to other approaches. The optimal scheme was thus using a random forest regression tree, combining climate, soil, and biological variables, and predicting PAGPP. The optimal scheme generating AGPP of Chinese terrestrial ecosystems decreased from southeast to northwest, which was highly consistent with previous products. The interannual trend and interannual variation of our generating AGPP showed a decreasing trend from east to west and from southeast to northwest, respectively, which was consistent with data-oriented products. The mean total amount of generated AGPP was 7.03 ± 0.45 PgC yr-1 falling into the range of previous works. Considering the consistency between the generated AGPP and previous products, our optimal mapping way was suitable for mapping AGPP from site measurements. Our results provided a methodological support for mapping regional AGPP and other fluxes.

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The urgent requirement of human society to solve major resource and environmental pro-blems at the regional and global scales promotes the rises of macroecosystem science (MES) and the multidisciplinary fusions of natural science and humanities. Furthermore, it facilitates the innovation of macroecosystem scientific theory, as well as the development of continental and global scale knowledge fusion methodology and key technology. With the aim to serve the construction and deve-lopment of continental and global scale knowledge fusion methodological system for the changes of ecosystem status and resource environmental effect studies, we systematically elaborated the multi-disciplinary dimensional basic scientific problems, logic relationships and frontiers in the macroecosystem science, discussed the ideology and content of constructing the continental and global scale research methodological system, proposed to develop the networked observation-networked experiment-numerical simulation-knowledge fusion four-in-one infrastructures. This study would provide theoretical references for the network design of ecosystem observation research in China and at the global scale.

[Minimally invasive percutaneous plate osteosynthesis for the treatment of acetabulum anterior column fracture with intact true pelvic brim].

OBJECTIVE: To discuss feasibility and clinical effects of minimally invasive percutaneous plate osteosynthesis in treating acetabulum anterior column fracture with intact true pelvic brim. METHODS: From May 2013 to December 2015, 8 patients with acetabulum anterior column fracture with intact true pelvic brim were reviewed retrospectively. According to Judet-Letournel classification, all were simple unstable acetabulum anterior column fracture. Among them, there were 5 males and 3 females with an average age of 42.8 years old ranging from 22 to 63. The injury was caused by crush in 4 cases, smash of heavy object in 3 cases, and falling down in 1 case. The time from injury to operation was ranged from 5 to 19 days with an average of 9.5 days. Preoperative CT showed high anterior column fracture of acetabulum with intact true pelvic brim, the fracture separation was less than 1 cm. All the patients were treated with closed reduction and minimally invasive percutaneous plate osteosynthesis. The quality of fracture reduction, operation time, blood loss, fracture healing time, hip function and postoperative complications were observed and recorded. RESULTS: All patients were followed up from 10 to 19 months with an average of 14.5 months. The quality of reduction was classified as anatomical in 4 patients, imperfect in 3, poor in 1 by Matta's score system. The operation time was 30 to 80 min, averaged 51.3 min;the blood loss was 50 to 120 ml, averaged 86.2 ml; fracture healing time was 10 to 19 weeks, averaged 13.3 weeks. At the latest follow-up, the hip function was evaluated by Merle D'Aubigne scoring system, 5 cases got excellent results, 2 cases in good, and 1 case in fair. No vascular nerve injury, wound infection, bleeding, deep vein thrombosis and other complications occurred in 8 patients. CONCLUSIONS: Minimally invasive percutaneous plate osteosynthesis in treating acetabulum anterior column fracture with intact true pelvic brim has advantages of less trauma, less bleeding, quick recovery and good curative effect, and it is a good surgical procedures for acetabulum anterior column fracture.

Study on the Adsorption Capacities for Airborne Particulates of Landscape Plants in Different Polluted Regions in Beijing (China).

Urban landscape plants are an important component of the urban ecosystem, playing a significant role in the adsorption of airborne particulates and air purification. In this study, six common landscape plants in Beijing were chosen as research subjects, and the adsorption capacities for each different plant leaf and the effects of the leaf structures for the adsorption capacities for particulates were determined. Preliminary results show that needle-leaved tree species adsorbed more airborne particulates than broad-leaved tree species for the same leaf area. Pinus tabuliformis exhibits the highest adsorption capacity, at 3.89 ± 0.026 µg·cm(-2), almost two times as much as that of Populus tomentosa (2.00 ± 0.118 µg·cm(-2)). The adsorption capacities for PM10 of the same tree species leaves, in different polluted regions had significant differences, and the adsorption capacities for PM10 of the tree species leaf beside the Fifth Ring Road were higher than those of the tree species leaves in the Botanical Garden, although the adsorption capacities for PM2.5 of the same tree species in different polluted regions had no significant differences. By determining the soluble ion concentrations of the airborne particulates in two regions, it is suggested that the soluble ion concentrations of PM10 in the atmosphere in the Botanical Garden and beside the Fifth Ring Road have significant differences, while those of PM2.5 in the atmosphere had no significant differences. In different polluted regions there are significant adaptive changes to the leaf structures, and when compared with slightly polluted region, in the seriously polluted region the epidermis cells of the plant leaves shrinked, the surface textures of the leaves became rougher, and the stomas' frequency and the pubescence length increased. Even though the plant leaves exposed to the seriously polluted region changed significantly, these plants can still grow normally and healthily.

[Adsorption Capacity of the Air Particulate Matter in Urban Landscape Plants in Different Polluted Regions of Beijing].

Urban landscape plants, as one of the important factors of the urban ecosystem, play an important role in stagnating airborne particulates and purifying urban atmospheric environment. In this article, six kinds of common garden plants were studied, and aerosol generator (QRJZFSQ-I) was used to measure the ability of their leaves to stagnate atmospheric particulates (TSP and PM2.5) in different polluted regions. Meanwhile, environmental scanning electron microscope was used to observe changes in the leaf structure of the tested tree species. The results showed: (1)Among the tested tree species, the ability of coniferous species to stagnate atmospheric particulates was higher than that of broad-leaved species per unit leaf area. Pinus tabuliformis stagnated the highest volume of (3. 89± 0. 026) µg . m-2, followed by Pinus bungeana of (2. 82 ± 0. 392) µg . cm-2, and Populus tomentosa stagnated the minimum of (2. 00 ± 0. 118) µg . cm-2; (2) Through observing the leaf microstructure morphology, coniferous species were found to have tightly packed stomas, stoma density and surface roughness higher than those of broad-leaved species, and they could also secrete oil; (3) In different polluted regions, the leaves of the same tree species showed significant difference in stagnating TSP. Per unit leaf area, the tree species leaves situated around the 5th Ring Road had higher ability to absorb TSP than the tree species leaves at Botanical Garden, while their abilities to absorb PM2.5 showed no significant difference; (4) In different polluted regions, significantly adaptive changes were found in leaf structure. Comparing to the region with light pollution, the outer epidermal cells of the plant leaves in region with heavy pollution shrank, and the roughness of the leaf skin textures as well as the stomatal frequency and villous length increased. In spite of the significant changes in plant leaves exposed to the heavy pollution, these plants could still maintain normal and healthy growth.

[Atmospheric Particle Retaining Function of Common Deciduous Tree Species Leaves in Beijing].

In order to explore the atmospheric particle-retaining function of common deciduous tree species leaves in Beijing, six typical tree species (Populus, Robinia pseudoacacia, Koelreuteria paniculata, Salix babylonica, Acer truncatum, Ginkgo biloba) were chosen to measure retaining amount of unit leaf area of air total suspended particles (TSP), coarse particles and fine particulate with aerosol generator (QRJZFSQ-I). The results showed that (1) All six tree species leaves had a certain level of retaining ability to different sizes of atmospheric particles, and different species exhibited some differences. For different sizes of atmospheric particle, retaining amounts of unit leaf area were higher in Koelreuteria paniculata and Robinia pseudoacacia than those of other four species, and the amount of Populus was the lowest among all tree species; (2) The retaining amount of unit leaf area for different tree species was not entirely increased with sampling time. The retaining amounts of TSP and coarse particles for all tree species on the eighth day after rain were significantly higher than those on the fifth day after rain, however, the retaining amount of fine particles was not significantly different under different sampling times. In order to select deciduous tree species for ecological management of air pollution in Beijing, Koelreuteria paniculata should be considered as the priority, followed by Robinia pseudoacacia, compared with Ginkgo biloba, Salix babylonica, Acer truncatum and Populus.

[Case-control studies on therapeutic effects of combined methods of minimally invasive percutaneous proximal humerus locked osteosynthesis plate with injectable bone for the treatment of proximal humerus fractures in elderly patients].

OBJECTIVE: To evaluate the clinical effects of combined methods of minimally invasive percutaneous proximal humeral internal locking system (PHILOS) and injectable bone for the treatment of proximal humerus fractures in elderly patients. METHODS: From January 2006 to January 2012, 80 patients with proximal humerus fractures were randomly divided into two groups (n = 40). The patients in the research group were treated with minimally invasive PHILOS fixation combined with injectable bone, including 20 males and 20 females, with an average age of (68.4 +/- 11.9) years; according to AO classification, 2 cases of type A1, 3 cases of type A2, 6 cases of type B1, 7 cases of type B2, 9 cases of type B3, 6 cases of type C1, 7 cases of type C2. The patients in the control group were treated with PHILOS fixation, including 18 males and 22 females, with an average age of (65.4 +/- 10.7) years; according to AO classification, 3 cases of type A1, 4 cases of type A2, 5 cases of type B1, 8 cases of type B2, 10 cases of type B3, 5 cases of type C, and 5 cases of type C2. The BMD, satisfactory rate, postoperative complications,bone healing time, Constant-Murley score in the two groups were reviewed and compared. RESULTS: In the research group, no patients had necrosis of femoral head, 1 patient had shoulder varus, 1 patient had internal fixation loosening, 36 patients were satisfactory with the treatment results, BMD was (1.013 +/- 0.109) g/cm2, bone healing time averaged (12.00 +/- 3.79) weeks, and the Constant-Murley score was 97.2 +/- 4.6. In the control group, 3 patients had necrosis of femoral head, 5 patients had shoulder varus, 6 patients had internal fixation loosening, 32 patients were satisfactory with the treatment results, BMD was (0.812 +/- 0.089) g/cm2, bone healing time averaged (20.00 +/- 8.67) weeks,and the Constant-Murley score was 78.5 +/- 3.2. The results of BMD, satisfactory rate, postoperative complications, bone healing time, and Constant-Murley score in the research group were better than those of control group (P < 0.05). CONCLUSION: PHILOS combined with injectable bone for the treatment of proximal humerus fractures in elderly patients has advantages of minimal wound, stable fixation, and earlier rehabilitation.

[Case-control study of influence factors analysis on short-term recovery after total knee arthroplasty in old patients with osteoarehritis].

OBJECTIVE: To investigate the relationship between variable influence factors and postoperative 2 week hospital special surgery (HSS) of knee joint, thus offer the treatment suggestion to patients with osteoarthritis, and judge the comprehensive effective prognosis to the clinical patient. METHODS: From March 2008 to August 2010, 72 patients with 72 knees were treated with TKA (treatment group), including 30 males and 42 females with a mean age of (71.9 +/- 6.2) years (ranged, 60 to 86 years). Twenty-two patients with HoldenIV OA treated by arthroscopy were in the control group, including 10 males and 12 females with a mean age of (70.5 +/- 5.9) years. The index including height, weight, BMI, muscle strength,knee joint HSS score and ROM were evaluated before operation and at 1st, 2nd weeks after operation. RESULTS: The HSS knee score and ROMs of patients in the treatment group improved. The pre-operative ROM, HSS score, knee pain, continous passive motion (CPM) at different level (i.e.CPM initial angle) had a prominent positive correlation with HSS score in postoperative 2 weeks. The factors such as patients' age, height, weight, BMI, muscular strength, etc. had no obvious relevant to HSS score in postoperative 2 weeks. CONCLUSION: The pre-operative HSS score, knee pain, knee ROM, perioperative severe complications, and postoperative CPM initial angle have a positive correlation with the postoperative effects.

Occurrence of cancer at multiple sites: towards distinguishing multigenesis from metastasis.

BACKGROUND: Occurrence of tumors at multiple sites is a hallmark of malignant cancers and contributes to the high mortality of cancers. The formation of multi-site cancers (MSCs) has conventionally been regarded as a result of hematogenous metastasis. However, some MSCs may appear as unusual in the sense of vascular dissemination pattern and therefore be explained by alternative metastasis models or even by non-metastatic independent formation mechanisms. RESULTS: Through literature review and incorporation of recent advance in understanding aging and development, we identified two alternative mechanisms for the independent formation of MSCs: 1) formation of separate tumors from cancer-initiating cells (CICs) mutated at an early stage of development and then diverging as to their physical locations upon further development, 2) formation of separate tumors from different CICs that contain mutations in some convergent ways. Either of these processes does not require long-distance migration and/or vascular dissemination of cancer cells from a primary site to a secondary site. Thus, we classify the formation of these MSCs from indigenous CICs (iCICs) into a new mechanistic category of tumor formation - multigenesis. CONCLUSION: A multigenesis view on multi-site cancer (MSCs) may offer explanations for some "unusual metastasis" and has important implications for designing expanded strategies for the diagnosis and treatment of cancers.

[Adult intestinal heterotopic gastric mucosa resulting in alimentary tract hemorrhage: a report of 11 cases].

OBJECTIVE: To investigate the clinical characteristics,diagnosis and treatment of intestinal heterotopic gastric mucosa resulting in alimentary tract hemorrhage. METHODS: Eleven cases of intestinal heterotopic gastric mucosa with alimentary tract hemorrhage during the past 24 years in our hospital were reviewed and the clinical data were analyzed retrospectively. RESULTS: The median age was 29 years old. Nine cases had abdominal pain, and radionuclide (99m)Tc-pertechnetate scan revealed bleeding lesion in 6 cases preoperatively. Segmental resection of the intestine with bleeding lesion were performed in all patients, postoperative pathology confirmed heterotopic gastric mucosa. The lesion was located in the jejunum in five cases and in the ileum in six cases. All lesions were complicated with diverticulum, or inflammatory mass on the intestinal wall, or abnormity of intestinal duplication. CONCLUSIONS: Intestinal heterotopic gastric mucosa is difficult to be diagnosed preoperatively, and radionuclide (99m)Tc-pertechnetate scan plays a role in preoperative diagnosis.