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.

Creating a Dual-Functional 2D Perovskite Layer at the Interface to Enhance the Performance of Flexible Perovskite Solar Cells.

Flexible perovskite solar cells (f-PSCs) have been attracting tremendous attention due to their potentially commercial prospects in flexible energy system and mobile energy system. Reducing the energy barriers and charge extraction losses at the interfaces between perovskite and charge transport layers is essential to improve both efficiency and stability of f-PSCs. Herein, 4-trifluoromethylphenylethylamine iodide (CF3 PEAI) is introduced to form a 2D perovskite at the interface between perovskite and hole transport layer (HTL). It is found that the 2D perovskite plays a dual-functional role in aligning energy band between perovskite and HTL and passivating the traps in the 3D perovskite, thus reducing energy loss and charge carrier recombination at the interface, facilitating the hole transfer from perovskite to the Spiro-OMeTAD. Consequently, the photovoltaic performance of f-PSCs is significantly improved, leading to a power conversion efficiency (PCE) of 21.1% and a certified PCE of 20.5%. Furthermore, the long-term stability of f-PSCs is greatly improved through the protection of 2D perovskite layer to the underlying 3D perovskite. This work provides an excellent strategy to produce efficient and stable f-PSCs, which will accelerate their potential applications.

Drop-Casting to Make Efficient Perovskite Solar Cells under High Humidity.

Drop-casting was used to make MAPbI3 films for solar cells. The crystal growth in drop-cast MAPbI3 films was regulated by adjusting temperature. A mechanism for the formation of different morphology was proposed by combining in situ crystal-growth study with XRD measurements. The crystals in the films made at low temperature (60 °C) and high temperature (≥120 °C) are (110) and (200) oriented, respectively. The different crystal growth mode leads to quite different film morphology. Compared with spin-coating, drop-casting shows much better tolerance to humidity. MAPbI3 solar cells made under 88 % humidity delivered a PCE of 18.17 %, which is the highest PCE for perovskite solar cells made under >70 % humidity without antisolvent assistance.

Controlling Homogenous Spherulitic Crystallization for High-Efficiency Planar Perovskite Solar Cells Fabricated under Ambient High-Humidity Conditions.

The influence of precursor solution properties, fabrication environment, and antisolvent properties on the microstructural evolution of perovskite films is reported. First, the impact of fabrication environment on the morphology of methyl ammonium lead iodide (MAPbI3 ) perovskite films with various Lewis-base additives is reported. Second, the influence of antisolvent properties on perovskite film microstructure is investigated using antisolvents ranging from nonpolar heptane to highly polar water. This study shows an ambient environment that accelerates crystal growth at the expense of nucleation and introduces anisotropies in crystal morphology. The use of antisolvents enhances nucleation but also influences ambient moisture interaction with the precursor solution, resulting in different crystal morphology (shape, size, dispersity) in different antisolvents. Crystal morphology, in turn, dictates film quality. A homogenous spherulitic crystallization results in pinhole-free films with similar microstructure irrespective of processing environment. This study further demonstrates propyl acetate, an environmentally benign antisolvent, which can induce spherulitic crystallization under ambient environment (52% relative humidity, 25 °C). With this, planar perovskite solar cells with ≈17.78% stabilized power conversion efficiency are achieved. Finally, a simple precipitation test and in situ crystallization imaging under an optical microscope that can enable a facile a priori screening of antisolvents is shown.

Association Between BMI and Recurrence of Primary Spontaneous Pneumothorax.

BACKGROUND: Whether body mass index (BMI) is a significant risk factor for recurrence of primary spontaneous pneumothorax (PSP) remains controversial. The purpose of this study was to examine whether BMI and other factors are linked to risk of PSP recurrence. METHODS: A consecutive cohort of 273 patients was retrospectively evaluated. Patients were divided into those who experienced recurrence (n = 81) and those who did not (n = 192), as well as into those who had low BMI (n = 75) and those who had normal or elevated BMI (n = 198). The two pairs of groups were compared in terms of baseline data, and Cox proportional hazards modeling was used to identify predictors of PSP recurrence. RESULTS: Rates of recurrence among all 273 patients were 20.9% at 1 year, 23.8% at 2 years, and 28.7% at 5 years. Univariate analysis identified the following significant predictors of PSP recurrence: height, weight, BMI, size of pneumothorax, and treatment modality. Multivariate analyses identified several risk factors for PSP recurrence: low BMI, pneumothorax size ≥50%, and non-surgical treatment. Kaplan-Meier survival analysis indicated that patients with low BMI showed significantly lower recurrence-free survival than patients with normal or elevated BMI (P < 0.001). CONCLUSIONS: Low BMI, pneumothorax size ≥50%, and non-surgical treatment were risk factors for PSP recurrence in our cohort. Low BMI may be a clinically useful predictor of PSP recurrence.

Effect of neoadjuvant chemoradiotherapy on perioperative immune function of patients with locally advanced esophageal cancer.

This study aims to evaluate the effect of neoadjuvant chemoradiotherapy (NCRT) on perioperative immune function during surgery to treat resectable locally advanced esophageal cancer. Records were retrospectively analyzed for 220 patients with locally advanced esophageal cancer, of whom 112 received surgery alone and 98 received neoadjuvant NCRT plus surgery. The two groups were compared in terms of proportions of CD3+, CD4+, CD8+, and natural kill (NK) cells, as well as the ratio of CD4+ to CD8+ cells. These measurements were made using flow cytometry on preoperative day 1 and on postoperative days 1 and 7. Subgroup analysis were performed in terms of degrees of pathological response of NCRT. When the entire NCRT and no-NCRT (surgery alone) cohorts were compared, no significant differences in propocrtions of CD3+, CD4+, CD8+, or NK cells or in the CD4+/CD8+ ratio occurred at any of the three time points. Similar results were obtained using the subgroup of NCRT patients who were NCRT-sensitive, but the subgroup of NCRT-insensitive patients showed significantly lower CD4+ and NK proportions and lower CD4+/CD8+ ratio than the no-NCRT group. Our findings suggest that NCRT does not affect perioperative immune function in patients who are NCRT-sensitive, but it does significantly reduce such function in patients who are NCRT-insensitive.

Lead-free Perovskite Materials (NH4 )3 Sb2 Ix Br9-x.

A family of perovskite light absorbers (NH4 )3 Sb2 Ix Br9-x (0≤x≤9) was prepared. These materials show good solubility in ethanol, a low-cost, hypotoxic, and environmentally friendly solvent. The light absorption of (NH4 )3 Sb2 Ix Br9-x films can be tuned by adjusting I and Br content. The absorption onset for (NH4 )3 Sb2 Ix Br9-x films changes from 558 nm to 453 nm as x changes from 9 to 0. (NH4 )3 Sb2 I9 single crystals were prepared, exhibiting a hole mobility of 4.8 cm2 V-1 s-1 and an electron mobility of 12.3 cm2 V-1 s-1 . (NH4 )3 Sb2 I9 solar cells gave an open-circuit voltage of 1.03 V and a power conversion efficiency of 0.51 %.

Solution-Processed Cu2O and CuO as Hole Transport Materials for Efficient Perovskite Solar Cells.

Solution-processed Cu2 O and CuO are used as hole transport materials in perovskite solar cells. The cells show significantly enhanced open circuit voltage Voc, short-circuit current Jsc, and power conversion efficiency (PCE) compared with PEDOT cells. A PCE of 13.35% and good stability are achieved for Cu2O cells, making Cu2O a promising material for further application in perovskite solar cells.

A fused-ring acceptor unit in d-a copolymers benefits photovoltaic performance.

Pentacyclic lactam acceptor unit TPTI invented by our group is proved to be a good building block for efficient D-A copolymers used in organic solar cells. Here, two D-A copolymers PBTTPTI and PTTTPTI are developed by copolymerizing TPTI with 2,2'-bithiophene (BT) or thieno[3,2-b]thiophene (TT). PBTTPTI and PTTTPTI exhibit good solubility and strong interchain π-π interaction even in dilute solution. They possess deep HOMO levels (ca. -5.3 eV), partial crystallinity, and good hole mobilities. Blending with PC71 BM, PBTTPTI and PTTTPTI give decent power conversion efficiencies (PCE) up to 6.83% and 5.86%, with outstanding fill factors (FF) of 74.3% and 71.3%, respectively.

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.

Optimizing the Buried Interface in Flexible Perovskite Solar Cells to Achieve Over 24% Efficiency and Long-Term Stability.

The buried interface of the perovskite layer has a profound influence on its film morphology, defect formation, and aging resistance from the outset, therefore, significantly affects the film quality and device performance of derived perovskite solar cells. Especially for FAPbI3 , although it has excellent optoelectronic properties, the spontaneous transition from the black perovskite phase to nonperovskite phase tends to start from the buried interface at the early stage of film formation then further propagate to degrade the whole perovskite. In this work, by introducing ─NH3 + rich proline hydrochloride (PF) with a conjugated rigid structure as a versatile medium for buried interface, it not only provides a solid α-phase FAPbI3 template, but also prevents the phase transition induced degradation. PF also acts as an effective interfacial stress reliever to enhance both efficiency and stability of flexible solar cells. Consequently, a champion efficiency of 24.61% (certified 23.51%) can be achieved, which is the highest efficiency among all reported values for flexible perovskite solar cells. Besides, devices demonstrate excellent shelf-life/light soaking stability (advanced level of ISOS stability protocols) and mechanical stability.

Synergistic Modification for Efficient Perovskite Solar Cells with Small Voltage Loss.

The power conversion efficiency (PCE) of perovskite solar cells has improved quickly in the past few years, but the PCE is still much lower than the theoretical limit. The relatively high energy loss (Eloss) is one of the critical factors limiting the PCE. To resolve the above issues, a synergistic modification strategy was used herein to minimize Eloss. RbCl and potassium polyacrylate (K-PAM) were used to modify the SnO2 layer. Additionally, Pb(Ac)2 was introduced into PbI2 to further improve the film quality. The synergistic modification strategy reduced the defects in SnO2 and perovskite and improved the energy-level alignment, enabling significantly reduced Eloss and enhanced photovoltaic performance. The best PCE of 24.07% was achieved, which was much higher than that of the control device (20.86%). The Eloss was only 0.349 eV for the target device. Good stability was achieved for the cells made using modified SnO2 and perovskite layers.

One-Step Gas-Solid-Phase Diffusion-Induced Elemental Reaction for Bandgap-Tunable CuaAgm1Bim2In/CuI Thin Film Solar Cells.

Lead-free inorganic copper-silver-bismuth-halide materials have attracted more and more attention due to their environmental friendliness, high element abundance, and low cost. Here, we developed a strategy of one-step gas-solid-phase diffusion-induced reaction to fabricate a series of bandgap-tunable CuaAgm1Bim2In/CuI bilayer films due to the atomic diffusion effect for the first time. By designing and regulating the sputtered Cu/Ag/Bi metal film thickness, the bandgap of CuaAgm1Bim2In could be reduced from 2.06 to 1.78 eV. Solar cells with the structure of FTO/TiO2/CuaAgm1Bim2In/CuI/carbon were constructed, yielding a champion power conversion efficiency of 2.76%, which is the highest reported for this class of materials owing to the bandgap reduction and the peculiar bilayer structure. The current work provides a practical path for developing the next generation of efficient, stable, and environmentally friendly photovoltaic materials.

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.

Fully Roll-to-Roll Processed Efficient Perovskite Solar Cells via Precise Control on the Morphology of PbI2:CsI Layer.

Perovskite solar cells (PSCs) have attracted tremendous attention as a promising alternative candidate for clean energy generation. Many attempts have been made with various deposition techniques to scale-up manufacturing. Slot-die coating is a robust and facile deposition technique that can be applied in large-area roll-to-roll (R2R) fabrication of thin film solar cells with the advantages of high material utilization, low cost and high throughput. Herein, we demonstrate the encouraging result of PSCs prepared by slot-die coating under ambient environment using a two-step sequential process whereby PbI2:CsI is slot-die coated first followed by a subsequent slot-die coating of organic cations containing solution. A porous PbI2:CsI film can promote the rapid and complete transformation into perovskite film. The crystallinity and morphology of perovskite films are significantly improved by optimizing nitrogen blowing and controlling substrate temperature. A power conversion efficiency (PCE) of 18.13% is achieved, which is promising for PSCs fabricated by two-step fully slot-die-coated devices. Furthermore, PSCs with a 1 cm2 area yield a champion PCE of 15.10%. Moreover, a PCE of 13.00% is obtained on a flexible substrate by the roll-to-roll (R2R) coating, which is one of the highest reported cells with all layers except for metal electrode fabricated by R2R process under ambient condition.

Modifying SnO2 with Polyacrylamide to Enhance the Performance of Perovskite Solar Cells.

Modification of the charge transport layers is an effective way to improve charge transport and performance of perovskite solar cells (PSCs). The ions in the ionic compounds used for the modification of SnO2 may migrate into the perovskite layer, which harms the stability of PSCs. In this work, a low-cost, water-soluble nonionic polymer polyacrylamide (PAM) is used to modify SnO2. The addition of PAM improves the uniformity, wettability, and electron mobility of the SnO2 film. Through the modification of SnO2, the defects of perovskite films are reduced and the grain size is increased. Furthermore, the energy-level alignment at the SnO2/perovskite interface is improved, which is beneficial to the transfer of electrons from perovskite to SnO2. Finally, the power conversion efficiency (PCE) of PSCs formed from modified SnO2 is enhanced to 22.59%. More importantly, the unencapsulated devices with modified SnO2 retain 90% of the initial value after storage for more than 1000 h under a relative humidity of 50%. These results indicate that modifying SnO2 using PAM is a promising strategy to improve the performance of PSCs.

4-Terminal Inorganic Perovskite/Organic Tandem Solar Cells Offer 22% Efficiency.

After fast developing of single-junction perovskite solar cells and organic solar cells in the past 10 years, it is becoming harder and harder to improve their power conversion efficiencies. Tandem solar cells are receiving more and more attention because they have much higher theoretical efficiency than single-junction solar cells. Good device performance has been achieved for perovskite/silicon and perovskite/perovskite tandem solar cells, including 2-terminal and 4-terminal structures. However, very few studies have been done about 4-terminal inorganic perovskite/organic tandem solar cells. In this work, semi-transparent inorganic perovskite solar cells and organic solar cells are used to fabricate 4-terminal inorganic perovskite/organic tandem solar cells, achieving a power conversion efficiency of 21.25% for the tandem cells with spin-coated perovskite layer. By using drop-coating instead of spin-coating to make the inorganic perovskite films, 4-terminal tandem cells with an efficiency of 22.34% are made. The efficiency is higher than the reported 2-terminal and 4-terminal inorganic perovskite/organic tandem solar cells. In addition, equivalent 2-terminal tandem solar cells were fabricated by connecting the sub-cells in series. The stability of organic solar cells under continuous illumination is improved by using semi-transparent perovskite solar cells as filter.

[Isolation and identification of side population cells in human lung adenocarcinoma cell line A549].

OBJECTIVE: To isolate and characterize the side population cells (SP cells) in the lung adenocarcinomas cell line A549. METHODS: The protein expression of ABCG2 in human lung adenocarcinoma cell line A549 was detected by immunohistochemistry. SP and NSP cells in the cell line A549 were isolated by FACS, and their differentiation was analysed. ABCG2 expression in the two cell subsets was detected by RT-PCR. The cell growth curves, cell division indexes, cell cycles, plate clone formation tests, migration and invasion assays, chemotherapeutic susceptibility tests, tests of the intracellular drug levels, and the tumor cell implantation experiments on nude mice were applied to study the biological properties of the two cell subsets. The expression of ABCG2 in the transplanted tumor in nude mice was detected by immunohistochemistry and RT-PCR. RESULTS: The positive rate of ABCG2 expression in the A549 cells by immunohistochemistry was 2.13%. SP and NSP cells were isolated by FACS. The SP cells could produce both SP and NSP cells, while NSP cells only produced NSP cells. SP cells expressed ABCG2, but NSP cells did not. The proliferation and migration abilities of the two cell subsets were similar, but the invasion and tumorigenic ability of SP cells was significantly higher than that of NSP cells. The susceptibilities to DDP and its intracellular levels of the two cell subsets were similar, but the susceptibilities to 5-FU, VP16, NVB and GEM and their intracellular levels of NSP cells were significantly higher than those of the SP cells. CONCLUSIONS: SP cells in the human lung adenocarcinomas cell line A549 is enriched with tumor stem cells. An effective way to get lung adenocarcinomas stem cells is to isolate SP cells by FACS.

Drop-Casting Method to Screen Ruddlesden-Popper Perovskite Formulations for Use in Solar Cells.

Small-area metal-halide perovskite solar cells (PSCs) having power-conversion efficiencies (PCEs) of greater than 25% can be prepared by using a spin-coated perovskite layer, but this technique is not readily transferrable to large-scale manufacturing. Drop-casting is a simple alternative method for film formation that is more closely aligned to industry-relevant coating processes. In the present work, drop-casting was used to prepare films for screening two-dimensional Ruddlesden-Popper (2DRP) metal-halide perovskite formulations for potential utility in PSCs, without additional processing steps such as inert-gas blowing or application of antisolvent. The composition of the 2DRP formulation used for drop-casting was found to have a profound effect on optical, spectroscopic, morphological, and phase-distribution properties of the films as well as the photovoltaic performance of related PSC devices. This facile method for screening film quality greatly assists in speeding up the identification of perovskite formulations of interest. The optimal 2DRP perovskite formulation identified from screening was utilized for industry-relevant one-step roll-to-roll slot-die coating on a flexible plastic substrate, producing PSCs having PCEs of up to 8.8%. A mechanism describing film formation and phase distribution in the films is also proposed.

Lead-Free Perovskite Photodetectors: Progress, Challenges, and Opportunities.

State-of-the-art photodetectors which apply hybrid perovskite materials have emerged as powerful candidates for next-generation light sensing. Among them, lead-based ones are the most popular beyond doubt on account of their unique and superior optoelectronic properties. Nevertheless, trade-off toward commercialization exists between nontoxicity and high performance, with the poor stability of lead-based perovskites, indicating that it is indispensable to substitute lead with nontoxic element meanwhile bringing about a comparable figure of merit of photodetectors and relatively long-term stability. Herein, recent advances in lead-free perovskite photodetectors are reviewed, analyzing the principle while designing new materials and highlighting some remarkable progress, which are comparable, even superior, to lead-based photodetectors. Furthermore, their potential strategy in optical communication, image sensing, narrowband photodetection, etc., is examined and a perspective on developing new materials and photodetectors with superior properties for more practical applications is provided.