Tethered Helical Ladder-Type Aromatic Lactams.

Tethered nonplanar aromatics (TNAs) make up an important class of nonplanar aromatic compounds showing unique features. However, the knowledge on the synthesis, structures, and properties of TNAs remains insufficient. In this work, a new type of TNAs, the tethered aromatic lactams, is synthesized via Pd-catalyzed consecutive intramolecular direct arylations. These molecules possess a helical ladder-type conjugated system of up to 13 fused rings. The overall yields ranged from 3.4 to 4.3%. The largest of the tethered aromatic lactams, 6L-Bu-C14, demonstrates a guest-adaptive hosting capability of TNAs for the first time. When binding fullerene guests, the cavity of 6L-Bu-C14 became more circular to better accommodate spherical fullerene molecules. The host-guest interaction is thoroughly studied by X-ray crystallography, theoretical calculations, fluorescence titration, and nuclear magnetic resonance (NMR) titration experiments. 6L-Bu-C14 shows stronger binding with C70 than with C60 due to the better convex-concave π-π interaction. P and M enantiomers of all tethered aromatic lactams show distinct and persistent chiroptical properties and demonstrate the potential of chiral TNAs as circularly polarized luminescence (CPL) emitters.

A 4-Arm Small Molecule Acceptor with High Photovoltaic Performance.

Manipulating the backbone of small molecule acceptors (SMAs) is of particular importance in developing efficient organic solar cells (OSCs). The common design is constructing 2-arm SMAs with linear or curved backbones. Herein, we report an acceptor 4A-DFIC with a 4-arm backbone unexpectedly generated in the reaction of an electron-rich aromatic diamine and hexaketocyclohexane. Single-crystal X-ray diffraction analysis indicates the rigid and twisted molecular plane and the effective molecular stacking of 4A-DFIC in solid state. 4A-DFIC shows a low band gap of 1.40 eV and excellent light-harvesting capability from visible to near-infrared region. Binary and ternary OSCs based on 4A-DFIC gave power conversion efficiencies (PCEs) of 15.76 % and 18.60 % (certified 18.1 %), respectively, which are the highest PCEs for multi-arm SMA-based OSCs to date.

Improving Photovoltaic Performance of a Fused-Ring Azepinedione Copolymer via a D-A-A Design.

Two conjugated copolymer donors, PTTABDT and PBTTABDT, based on a fused-ring azepinedione acceptor unit, 5-(2-octyldodecyl)-4H-thieno[2',3':4,5]thieno[3,2-c]thieno[2',3':4,5]thieno[2,3-e]azepine-4,6(5H)-dione (TTA), are prepared. PTTABDT possesses a conventional donor-acceptor (D-A) structure with one TTA in the repeat unit, while PBTTABDT has a D-A-A structure with two TTAs in the repeat unit. Compared with PTTABDT, PBTTABDT shows a deeper highest occupied molecular orbital (HOMO) level, a narrower bandgap, and a higher hole mobility, and exhibits better performance in bulk heterojunction solar cells. Power conversion efficiencies of 6.18% and 7.81% are achieved from PTTABDT:PC71 BM and PBTTABDT:PC71 BM solar cells, respectively. The higher performance of PBTTABDT:PC71 BM solar cells results from the enhanced open-circuit voltage (V oc ) and short-circuit current density ( J sc ).

Hydroxy-Al and cell-surface negativity are responsible for the enhanced sensitivity of Rhodotorula taiwanensis to aluminum by increased medium pH.

Aluminum (Al) is ubiquitous and toxic to microbes. High Al3+ concentration and low pH are two key factors responsible for Al toxicity, but our present results contradict this idea. Here, an Al-tolerant yeast strain Rhodotorula taiwanensis RS1 was incubated in glucose media containing Al with a continuous pH gradient from pH 3.1-4.2. The cells became more sensitive to Al and accumulated more Al when pH increased. Calculations using an electrostatic model Speciation Gouy Chapman Stern indicated that, the increased Al sensitivity of cells was associated with AlOH2+ and Al(OH) 2+ rather than Al3+. The alcian blue (a positively charged dye) adsorption and zeta potential determination of cell surface indicated that, higher pH than 3.1 increased the negative charge and Al adsorption at the cell surface. Taken together, the enhanced sensitivity of R. taiwanensis RS1 to Al from pH 3.1-4.2 was associated with increased hydroxy-Al and cell-surface negativity.

Surgical Treatment of Acute Grade III Medial Collateral Ligament Injury Combined With Anterior Cruciate Ligament Injury: Anatomic Ligament Repair Versus Triangular Ligament Reconstruction.

PURPOSE: The purpose of this study was to evaluate the clinical results of medial collateral ligament (MCL) anatomic ligament repair (ALR) and triangular ligament reconstruction (TLR) in treating acute grade III MCL injury with respect to imaging and functional results. METHODS: Between January 2009 and October 2011, a total of 69 patients with an acute grade III MCL tear combined with an anterior cruciate ligament tear were divided into 2 groups: those who underwent ALR and those who underwent TLR. Single-bundle anterior cruciate ligament reconstruction was also performed in all patients. A radiographic stress-position imaging test was performed to evaluate excessive medial opening of the knee. In addition, the Slocum test was carried out to assess anteromedial rotatory instability before surgery and at follow-up. The subjective symptoms and functional outcomes were evaluated preoperatively and postoperatively with International Knee Documentation Committee (IKDC) assessment. RESULTS: Sixty-four patients with a mean follow-up period of 34 months were included in the final analysis. The measurement results for medial opening at the last follow-up appointment decreased significantly from the pretreatment measurements and fell within the normal range, without a statistically significant difference between the 2 groups (P > .05). The overall incidence of anteromedial rotatory instability was reduced to 21.9% compared with 62.5% preoperatively. However, the incidence of anteromedial rotatory instability in the TLR group (9.4%) decreased significantly compared with that in the ALR group (34.4%) (P < .05). All patients' IKDC subjective scores significantly improved after surgery. No statistically significant difference was found between the 2 groups at the last follow-up (P > .05). The comparison of IKDC extension and flexion deficit scores between the 2 groups showed no significant differences. Eleven patients in the ALR group and 4 in the TLR group complained of medial knee pain. The comparison between the 2 groups showed no significant difference (P > .05). CONCLUSIONS: The clinical outcomes of this study showed that no major difference existed in the ALR and TLR groups based on IKDC scores and medial opening evaluations in the short-term. However, TLR offered better rotatory stability than ALR at final follow-up. LEVEL OF EVIDENCE: Level II, lesser-quality randomized controlled trial.

Incidence of deep venous thrombosis in Chinese patients undergoing arthroscopic knee surgery for cruciate ligament reconstruction.

PURPOSE: This study investigated the incidence of deep venous thrombosis (DVT) in patients undergoing arthroscopic cruciate ligament surgery. METHODS: A total of 282 patients were examined by color Doppler ultrasound preoperatively and 3 and 7 days postoperatively. RESULTS: DVT was present in 34 of 282 patients (12.1 %); of these, 11 (32.6 %) underwent reconstruction of the anterior cruciate ligament (ACL), alone or in conjunction with the medial or lateral collateral ligament (MCL or LCL, respectively; 17.6 %); eight (23.5 %) of the posterior cruciate ligament (PCL); four (11.8 %) of the PCL-MCL/LCL; and five (14.7 %) of the ACL-MCL. In patients with tourniquets applied for <90, 90-120, and >120 min, the incidence of DVT was 5.6, 12.8, and 17.4 %, respectively. CONCLUSION: The incidence of DVT in normal patients undergoing ACL surgery was 12.1 %. A higher incidence was observed among cases of multiligament reconstruction, especially those involving the PCL, as well as in patients with tourniquets applied for more than 2 h. Based on these findings, prophylactic measures for DVT may be considered after arthroscopic knee surgery in order to decrease the incidence of DVT if specific risk factors are present. LEVELS OF EVIDENCE: IV.

A highly efficient fullerene acceptor for polymer solar cells.

C70-based acceptors show great potential in polymer solar cells (PSCs). Two high-LUMO C70 acceptors, the 66π OQMF70 and the 64π bis-OQMF70, based on methano[70]fullerene (C70CH2) were developed. An outstanding power conversion efficiency (PCE) of 6.88% was obtained from OQMF70:P3HT solar cells.

A dumbbell-like A-D-A molecule for single-component organic solar cells.

A dumbbell-like A-D-A molecule, triad 1, containing a dithienosilole-dibenzothiadiazole donor unit and two fullerene acceptor units was designed and synthesized. Triad 1 shows good solubility, thermostability, light absorbance, and film-forming capability. Solar cells using 1 as the active layer gave a PCE of 0.4%.

Xanthone glycosides from Swertia bimaculata with α-glucosidase inhibitory activity.

Seven new xanthone glycosides (1-7) were isolated from the n-butanol extract of Swertia bimaculata, together with six known compounds (8-13). Their structures were elucidated on the basis of extensive spectroscopic analyses (1D- and 2D-NMR, HRESIMS, UV, and IR) and comparison with data reported in the literature. All the compounds were evaluated for their α-glucosidase inhibitory activities in vitro, and compounds 3, 4, and 7 exhibited significant activities to inhibit α-glucosidase. Meanwhile the effects of different substitutions on the α-glucosidase inhibitory activity of xanthone glycosides from S. bimaculata are also discussed.

Polysaccharides from Liriopes Radix ameliorates hyperglycemia via various potential mechanisms in diabetic rats.

BACKGROUND: Liriopes Radix, which is regarded as both drug and healthy diet, is drunk as tea and used in traditional Chinese medicine to treat diabetes. Based on our previous studies, investigated the hypoglycemic effects and explored the mechanisms of total polysaccharides from Liriope spicata var. prolifera (Liriopes Radix) in a diabetic rat model. RESULTS: TLSP reduced hyperglycemia in diabetic rats. The oral glucose tolerance test showed that TLSP could improve the glucose tolerance of diabetic rats. Damage to liver and pancreas tissue was inhibited after treatment with TLSP. Moreover, TLSP increased glycogen content, glucokinase (GK) and glycogen synthetase (GS) activities, and suppressed the elevation of glucose-6-phosphatase (G6Pase) and glycogen phosphorylase (GP) activities in liver. Compared with the diabetic control group, GK and GS mRNA expression were significantly elevated, while G6Pase and GP mRNA expression were decreased in TLSP groups. In addition, TLSP could inhibit glycogen synthase kinase-3ß expression and increase insulin receptor, insulin receptor substrate-1, phosphoinositide 3-kinase, protein kinase B and glucose transport protein-4 expression in liver. CONCLUSION: TLSP showed hypoglycemic function. Improvement of glucose metabolism and insulin-signaling transduction were possible mechanisms.

[Noninvasive detection of hematocrit and the mean corpuscular hemoglobin concentration levels by Vis-NIR spectroscopy].

Hematocrit (HCT) and mean hemoglobin concentration(MCHC) play a very important role in preventing cardiovascular disease and anemia. A method was developed on the basis of spectroscopy to detect HCT and MCHC non-invasively and accurately. The anatomical study showed that the blood rheology abnormalities and blood viscosity's changes can cause the changes of tongue, so there is a certain correlation between tongue and blood components. Reflectance spectrums from the tongue tips of 240 volunteers were collected, then the tongue pictures were captured and the biochemical analysis results were recorded at the same time. The 240 samples were separated into two parts: calibration sample and test sample. Spectra were then subjected to a partial least squares regression (PLSR) analysis to develop mathematics models for predicting HCT levels. The correlation between the data and prediction of HCT and MCHC yielded calibration samples value of 0.998 and 0.938. HCT and MCHC levels of test samples predicted by this model from Visible-Near infrared spectra provided a coefficient of determination in prediction of 0.979 and 0.883 with an average relative error of prediction of 1.65% and 1.88%, a root mean square error of prediction of 4.066 and 4.139. From the experiment results we can see that the model which was built before can better predict the HCT and MCHC, and the results also showed that spectrometry method may provide a promising approach to the noninvasive measurement of human HCT and MCHC with a combination of PLSR analysis.

[Characteristics analysis of human tongue reflectance spectra].

The present paper presents the spectroscopic analysis method. Eighty samples of spectra data of tongue parts with coating and without coating were collected by Usb4000 spectrometer of Ocean Optics, then comparing the spectra data of the different parts of tongue we found that there was a relation between the spectra characteristics and tongue coating, and further analysis of the spectra data showed that there was a big difference between the two parts within the wavelength range between 500 and 600 nm. It was also found that the biggest differences appear when the wavelength is 579.39 nm, and at the same time, different colors of tongue coating were also compared, and the spectrum was also quite different because of different color and thickness of the tongue coating. The experiment results show that different color, thickness, and dryness of the human tongue coating lead to different spectral characteristics, and compared with the current colorimetric method of tongue characterization, spectral reflectance can reflect more physiological and pathological information. The experiment results also indicated that the different spectral characteristics of tongue property and tongue coating will be used for further separation of these two parts, and to provide an objective analysis index for tongue coating qualitative and quantitative analysis, so as to promote the objectivity of the TCM.

The Development of Quinoxaline-Based Electron Acceptors for High Performance Organic Solar Cells.

In the recent advances of organic solar cells (OSCs), quinoxaline (Qx)-based nonfullerene acceptors (QxNFAs) have attracted lots of attention and enabled the recorded power conversion efficiency approaching 20%. As an excellent electron-withdrawing unit, Qx possesses advantages of many modifiable sites, wide absorption range, low reorganization energy, and so on. To develop promising QxNFAs to further enhance the photovoltaic performance of OSCs, it is necessary to systematically summarize the QxNFAs reported so far. In this review, all the focused QxNFAs are classified into five categories as following: SM-Qx, YQx, fused-YQx, giant-YQx, and polymer-Qx according to the molecular skeletons. The molecular design concepts, relationships between the molecular structure and optoelectronic properties, intrinsic mechanisms of device performance are discussed in detail. At the end, the advantages of this kind of materials are summed up, the molecular develop direction is prospected, the challenges faced by QxNFAs are given, and constructive solutions to the existing problems are advised. Overall, this review presents unique viewpoints to conquer the challenge of QxNFAs and thus boost OSCs development further toward commercial applications.

Asymmetric Π-Bridge Engineering Enables High-Permittivity Benzo[1,2-B:4,5-b']Difuran-Conjugated Polymer for Efficient Organic Solar Cells.

Organic solar cells (OSCs) exhibit complex charge dynamics, which are closely correlated with the dielectric constant (ɛr ) of photovoltaic materials. In this work, a series of novel conjugated copolymers based on benzo[1,2-b:4,5-b']difuran (BDF) and benzotriazole (BTz) is designed and synthesized, which differ by the nature of π-bridge from one another. The PBDF-TF-BTz with asymmetric furan and thiophene π-bridge demonstrates a larger ɛr of 4.22 than PBDF-dT-BTz with symmetric thiophene π-bridge (3.15) and PBDF-dF-BTz with symmetric furan π-bridge (3.90). The PBDF-TF-BTz also offers more favorable molecular packing and appropriate miscibility with non-fullerene acceptor Y6 than its counterparts. The corresponding PBDF-TF-BTz:Y6 OSCs display efficient exciton dissociation, fast charge transport and collection, and reduced charge recombination, eventually leading to a power conversion efficiency of 17.01%. When introducing a fullerene derivative (PCBO-12) as a third component, the PBDF-TF-BTz:Y6:PCBO-12 OSCs yield a remarkable FF of 80.11% with a high efficiency of 18.10%, the highest value among all reported BDF-polymer-based OSCs. This work provides an effective approach to developing high-permittivity photovoltaic materials, showcasing PBDF-TF-BTz as a promising polymer donor for constructing high-performance OSCs.

A pyridine-functionalized pyrazolinofullerene used as a buffer layer in polymer solar cells.

A pyridine-functionalized pyrazolinofullerene (1) was synthesized in 42% yield via an improved one-pot reaction of C60, 3,6-di(2-pyridyl)-1,2,4,5-tetrazine, and water. The structure of 1 was unambiguously determined by X-ray diffraction of its single crystal. Due to the coordination capability of the functional groups on fullerene, compound 1 was used as a buffer layer to modify ZnO in inverted polymer solar cells. The power conversion efficiency was improved from 3.65% to 4.18% for inverted P3HT:PC61BM solar cells.

Donor-acceptor conjugated polymers based on a pentacyclic aromatic lactam acceptor unit for polymer solar cells.

A series of donor­acceptor (D­A) conjugated polymers P1­P4 was synthesized by copolymerization of a novel pentacyclic aromatic lactam acceptor unit, thieno[20,30:5,6]pyrido[3,4-g]thieno[3,2-c]-isoquinoline-5,11(4H,10H)-dione (TPTI), with a donor unit, benzo-[1,2-b:4,5-b0]dithiophene (BDT) or dithieno[3,2-b:20,30-d]silole (DTS). The effect of the donor units and the side chains on TPTI on polymer properties and solar cell performance was investigated. Bulk heterojunction solar cells based on P1 and PC71BM afforded the highest power conversion efficiency (PCE) of 5.30%.

High-Yield Gold Nanohydrangeas on Three-Dimensional Carbon Nanotube Foams for Surface-Enhanced Raman Scattering Sensors.

Recently, carbon nanomaterial-supported plasmonic nanocrystals used as high-performance surface-enhanced Raman scattering (SERS) substrates have attracted increasing attention due to their ultra-high sensitivity of detection. However, most of the work focuses on the design of 2-D planar substrates with traditional plasmonic structures, such as nanoparticles, nanorods, nanowires, and so forth. Here, we report a novel strategy for the preparation of high-yield Au nanohydrangeas on three-dimensional porous polydopamine (PDA)/polyvinyl alcohol (PVA)/carbon nanotube (CNT) foams. The structures and growth mechanisms of these specific Au nanocrystals are systematically investigated. PDA plays the role of both a reducing agent as well as an anchoring site for Au nanohydrangeas' growth. We also show that the ratio of surfactant KBr to the gold precursor (HAuCl4) is key to obtain these structures in a manner of high production. Moreover, the substrate of the CNT foam-Au nanohydrangea hybrid can be employed as SERS sensors and can detect the analytes down to 10-9 M.

PDMS/magnetic lignin sponge for oil/water separation.

Recyclable, non-toxic, and degradable biological substrates contribute significantly to super-wetting surfaces. In this work, we prepared magnetic micro-nano super-hydrophobic surfaces through a robust solution with magnetic modified lignin particles as the supporting structure. A novel PDMS (polydimethylsiloxane)/magnetic lignin particle (lignin@Fe3O4)/PDA sponge composite was fabricated. Through dopamine (DA) self-polymerization, covalent deposition of magnetic lignin (ML), and PDMS silane modification, the magnetic super-hydrophobic polyurethane sponge composite (Sponge-P) was synthesized so that the Fe3O4 nanoscale microspheres wrapped with microscale lignin magnetic particles adhered to the sponge surface tighter and were barely dislodged. The as-prepared Sponge-P displayed excellent flexibility and a water contact angle of up to 152.2°. The super-hydrophobic sponge prepared with the proposed method was acid-base stable (pH = 2-12), self-cleaning, and suitable for high-salinity seawater. The magnetic super-hydrophobic sponge has good oil-water separation ability and can absorb 43 times its own weight of oil. In the meantime, due to the introduction of magnetic materials into lignin, we not only constructed micro-nanostructures to improve the surface super-hydrophobicity, but also made Sponge-P have the function of magnetic recovery, which has a unique advantage in treating oily wastewater.

Solitary Scapular Metastasis as the First Presentation of Prostate Adenocarcinoma Identified on 99mTc-MDP SPECT/CT.

ABSTRACT: Metastases of prostate carcinoma in the skeleton are usually multiple. Solitary metastasis in appendicular skeleton is extremely rare. We present bone scan findings of solitary scapular metastasis from prostate adenocarcinoma as the initial presentation of his malignancy in a 62-year-old man. The 99mTc-MDP SPECT/CT demonstrated intense activity in the coracoid process of left scapula, whereas the tracer uptakes in other bones were not typical of metastases. The subsequent pathological results of the punctured left scapula confirmed as metastasis from prostate adenocarcinoma.

Self-Generated Buried Submicrocavities for High-Performance Near-Infrared Perovskite Light-Emitting Diode.

Embedding submicrocavities is an effective approach to improve the light out-coupling efficiency (LOCE) for planar perovskite light-emitting diodes (PeLEDs). In this work, we employ phenethylammonium iodide (PEAI) to trigger the Ostwald ripening for the downward recrystallization of perovskite, resulting in spontaneous formation of buried submicrocavities as light output coupler. The simulation suggests the buried submicrocavities can improve the LOCE from 26.8 to 36.2% for near-infrared light. Therefore, PeLED yields peak external quantum efficiency (EQE) increasing from 17.3% at current density of 114 mA cm-2 to 25.5% at current density of 109 mA cm-2 and a radiance increasing from 109 to 487 W sr-1 m-2 with low rolling-off. The turn-on voltage decreased from 1.25 to 1.15 V at 0.1 W sr-1 m-2. Besides, downward recrystallization process slightly reduces the trap density from 8.90 × 1015 to 7.27 × 1015 cm-3. This work provides a self-assembly method to integrate buried output coupler for boosting the performance of PeLEDs.