In situ observation of thermal-driven structural transitions of a ß-NaYF4 single nanoparticle aided with correlative cathodoluminescence electron microscopy.

NaYF4 systems have been widely studied as up-conversion host matrices, and their phase transitions are flexible and worth investigating in great detail. Herein, the evolution of morphology and crystal structure of a Eu3+-doped ß-NaYF4 single nanoparticle heated in an air atmosphere was investigated using in situ transmission electron microscopy (TEM). The annealing process revealed that the hexagonal ß-NaYF4 phase undergoes sequential transformations into high-temperature cubic phases at both 350 °C and 500 °C. The emission characteristics of Eu3+ in the single nanoparticle after heating treatment were also analyzed using Correlative Cathodoluminescence Electron Microscopy (CCLEM). The results of CCLEM suggest a gradual decrease followed by a subsequent increase in structural symmetry. A comprehensive spectroscopic and structural analysis encapsulates the entire transformation process as NaYF4 → YOF → Y2O3. In situ energy dispersive spectroscopy analyses (EDS) support this reaction process. The aforementioned technique yields correlative lattice-resolved TEM images and nanoscale spectroscopic information, which can be employed to assess the structure-function relationships on the nanoscale.

Preimmunization with Listeria-vectored cervical cancer vaccine candidate strains can establish specific T-cell immune memory and prevent tumorigenesis.

BACKGROUND: Although HPV prophylactic vaccines can provide effective immune protection against high-risk HPV infection, studies have shown that the protective effect provided by them would decrease with the increased age of vaccination, and they are not recommended for those who are not in the appropriate age range for vaccination. Therefore, in those people who are not suitable for HPV prophylactic vaccines, it is worth considering establishing memory T-cell immunity to provide long-term immune surveillance and generate a rapid response against lesional cells to prevent tumorigenesis. METHODS: In this study, healthy mice were preimmunized with LM∆E6E7 and LI∆E6E7, the two Listeria-vectored cervical cancer vaccine candidate strains constructed previously by our laboratory, and then inoculated with tumor cells 40 d later. RESULTS: The results showed that preimmunization with LM∆E6E7 and LI∆E6E7 could establish protective memory T-cell immunity against tumor antigens in mice, which effectively eliminate tumor cells. 60% of mice preimmunized with vaccines did not develop tumors, and for the remaining mice, tumor growth was significantly inhibited. We found that preimmunization with vaccines may exert antitumor effects by promoting the enrichment of T cells at tumor site to exert specific immune responses, as well as inhibiting intratumoral angiogenesis and cell proliferation. CONCLUSION: Altogether, this study suggests that preimmunization with LM∆E6E7 and LI∆E6E7 can establish memory T-cell immunity against tumor antigens in vivo, which provides a viable plan for preventing tumorigenesis and inhibiting tumor progression.

Discovery of novel reversible inhibitor of DprE1 based on benzomorpholine for the treatment of tuberculosis.

About a quarter of the world's population is infected with Mycobacterium tuberculosis, equivalent to about two billion people. With the emergence of multidrug-resistant tuberculosis, those existing anti-tuberculosis drugs no longer meet the demand for cure anymore; there is an urgent need for the development of new anti-tuberculosis drugs. Decaprenylphosphoryl-ß-D-ribose 2´-epimerase (DprE1) has been proven to be a potential antimycobacterial target, and several inhibitors have entered clinical trial. Herein, we designed and synthesized a series of compounds based on the indole and benzomorpholine by using the strategy of scaffold hopping. The preferred compound B18 showed strong antimycobacterial activity in H37Rv and drug-resistant clinical isolates. In addition, compound B18 did not exhibit antimycobacterial efficacy against other species of strains. Subsequently, the target of B18 was identified as DprE1 by analyzing spontaneous compound-resistant mutation data, and a docking study was performed to illustrate the binding mode between B18 and DprE1. In general, compound B18 is compatible to current DprE1 inhibitors, even higher phosphodiesterase 6C selectivity and plasma protein binding rate, which represent a new type of effective reversible DprE1 inhibitor. IMPORTANCE Drug therapy remains the cornerstone of tuberculosis (TB) treatment, yet first-line anti-tuberculosis drugs are associated with significant adverse effects that can compromise patient outcomes. Moreover, prolonged and widespread use has led to an alarming rise in drug-resistant strains of Mycobacterium tuberculosis, including multidrug-resistant [MDR-tuberculosis (TB)] and extensively drug-resistant (XDR-TB) forms. Urgent action is needed to develop novel anti-tuberculosis agents capable of overcoming these challenges. We report that compound B18, a decaprenylphosphoryl-ß-D-ribose 2´-epimerase inhibitor with a benzomorpholine backbone, exhibits potent activity against not only the non-pathogenic strain H37Ra, but also the pathogenic strain H37Rv and clinical MDR and XDR strains. Preliminary druggability studies indicate that B18 possesses high safety and acceptable pharmacokinetic properties, rendering it a promising candidate for further development as a novel anti-tuberculosis agent.

Bridging the Buried Interface with Piperazine Dihydriodide Layer for High Performance Inverted Solar Cells.

Given that it is closely related to perovskite crystallization and interfacial trap densities, buried interfacial engineering is crucial for creating effective and stable perovskite solar cells. Compared with the in-depth studies on the defect at the top perovskite interface, exploring the defect of the buried side of perovskite film is relatively complicated and scanty owing to the non-exposed feature. Herein, the degradation process is probed from the buried side of perovskite films with continuous illumination and its effects on morphology and photoelectronic characteristics with a facile lift-off method. Additionally, a buffer layer of Piperazine Dihydriodide (PDI2 ) is inserted into the imbedded bottom interface. The PDI2 buffer layer is able to lubricate the mismatched thermal expansion between perovskite and substrate, resulting in the release of lattice strain and thus a void-free buried interface. With the PDI2 buffer layer, the degradation originates from the growing voids and increasing non-radiative recombination at the imbedded bottom interfaces are suppressed effectively, leading to prolonged operation lifetime of the perovskite solar cells. As a result, the power conversion efficiency of an optimized p-i-n inverted photovoltaic device reaches 23.47% (with certified 23.42%) and the unencapsulated devices maintain 90.27% of initial efficiency after 800 h continuous light soaking.

Effect of Panax quinquefolius extract on Mycobacterium abscessus biofilm formation.

Mycobacterium abscessus (M. abscessus) can exist either as planktonic bacteria or as a biofilm. Biofilm formation is one of the important causes of conversion to resistance to antibiotics of bacteria that were previously sensitive when in their planktonic form, resulting in infections difficult to manage. Panax quinquefolius and its active ingredient ginsenosides have the potential ability in fighting pathogenic infections. In this study, the P. quinquefolius extract (PQE) showed good antibacterial/bactericidal activity against the M. abscessus planktonic cells. The extract reduced the biomass, thickness, and number of M. abscessus in the biofilm and altered its morphological characteristics as well as the spatial distribution of dead/alive bacteria. Moreover, the ginsenoside CK monomer had a similar inhibitory effect on M. abscessus planktonic bacteria and biofilm formation. Therefore, PQE and its monomer CK might be potential novel antimicrobial agents for the clinical prevention and treatment of M. abscessus, including biofilms in chronic infections.

Rinsing Intermediate Phase Strategy for Modulating Perovskite Crystal Growth and Fabricating Highly Efficient and Stable Inverted Solar Cells.

During the fabrication of metal halide perovskite films, polycrystal growth and maturation are largely influenced by high-temperature annealing. However, this process would cause crystals to expand or contract at various depths in the film, leading to microscopic structural deformation and further altering the optoelectronic properties of the perovskite film. Herein, we propose an additional rinsing intermediate phase (RIP) strategy that involves precovering the perovskite film surface with a mixed organic layer prior to high-temperature annealing. The lattice distortion of the microscopic structure brought on by the driving force of the heat field is greatly reduced as a result of the modulation for the upper surface of the intermediate phase film by the rinse layer. This strategy can prepare films with high crystallinity, minor residual stresses, fewer defects, and overall film uniformity. As a result, the modified inverted perovskite solar cell (PSC) achieves a certified power conversion (PCE) of 22.76%. Meanwhile, since the rinse layer is involved in the entire crystal formation process, ion migration and buildup in the device are prevented between the interface. Consequently, the devices still retain 90% of their initial PCE, demonstrating enhanced operational stability after 500 h of operation. This method of modulating the intermediate perovskite state offers an investigation into improving the traditional method of making thin films, which is anticipated to hasten the commercialization of perovskite photovoltaics.

Improved Conventional and New Approaches in the Diagnosis of Tuberculosis.

Tuberculosis (TB) is a life-threatening infectious disease caused by Mycobacterium tuberculosis (M. tuberculosis). Timely diagnosis and effective treatment are essential in the control of TB. Conventional smear microscopy still has low sensitivity and is unable to reveal the drug resistance of this bacterium. The traditional culture-based diagnosis is time-consuming, since usually the results are available after 3-4 weeks. Molecular biology methods fail to differentiate live from dead M. tuberculosis, while diagnostic immunology methods fail to distinguish active from latent TB. In view of these limitations of the existing detection techniques, in addition to the continuous emergence of multidrug-resistant and extensively drug-resistant TB, in recent years there has been an increase in the demand for simple, rapid, accurate and economical point-of-care approaches. This review describes the development, evaluation, and implementation of conventional diagnostic methods for TB and the rapid new approaches for the detection of M. tuberculosis.

Anti-tuberculosis drug development via targeting the cell envelope of Mycobacterium tuberculosis.

Mycobacterium tuberculosis possesses a dynamic cell envelope, which consists of a peptidoglycan layer, a mycolic acid layer, and an arabinogalactan polysaccharide. This envelope possesses a highly complex and unique structure representing a barrier that protects and assists the growth of M. tuberculosis and allows its adaptation to the host. It regulates the immune response of the host cells, causing their damage. Therefore, the cell envelope of M. tuberculosis is an attractive target for vaccine and drug development. The emergence of multidrug-resistant as well as extensively drug resistant tuberculosis and co-infection with HIV prevented an effective control of this disease. Thus, the discovery and development of new drugs is a major keystone for TB treatment and control. This review mainly summarizes the development of drug enzymes involved in the biosynthesis of the cell wall in M. tuberculosis, and other potential drug targets in this pathway, to provide more effective strategies for the development of new drugs.

Optimization of a SnO2-Based Electron Transport Layer Using Zirconium Acetylacetonate for Efficient and Stable Perovskite Solar Cells.

SnO2 is a promising material for use as an electron transfer layer (ETL) in perovskite photovoltaic devices due to its suitable energy level alignment with the perovskite, high electron mobility, excellent optical transmission, and low-temperature processability. The development of high-quality SnO2 ETLs with a large coverage and that are pinhole-free is crucial to enhancing the performance and stability of the perovskite solar cells (PSCs). In this work, zirconium acetylacetonate (ZrAcac) was introduced to form a double-layered ETL, in which an ideal cascade energy level alignment is obtained. The surface of the resulting ZrAcac/SnO2 (Zr-SnO2) layer is compact and smooth and had a high coverage of SnO2, which enhances the electron extractability, improves ion blocking, and reduces the charge accumulation at the interface. As a result, the fill factor (FF, 80.99%), power conversion efficiency (PCE, 22.44%), and stability of the Zr-SnO2 device have been significantly improved compared to PSCs with only a SnO2 ETL. In addition, the PCE of the Zr-SnO2 device is maintained at more than 80% of the initial efficiency after 500 h of continuous illumination.

Smart Strategy: Transparent Hole-Transporting Polymer as a Regulator to Optimize Photomultiplication-type Polymer Photodetectors.

Photomultiplication-type polymer photodetectors (PM-PPDs) were fabricated with hole-only transport active layers containing polymer(s): [6,6]-phenylC61-butyric acid methyl ester (PC61BM) with a weight ratio of 100:2. The rather less PC61BM content in active layers prefers to generate a large amount of isolated electron traps surrounded by polymers. Photogenerated electrons prefer to be trapped by the isolated PC61BM due to the lack of continuous electron-transport channels. The trapped electrons by the isolated PC61BM close to the Al electrode would like to seduce hole tunneling injection. The transparent polymer poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine] (poly-TPD) was incorporated as a regulator to improve hole mobility (µh) and adjust the trapped-electron distribution in active layers, leading to the enhanced performance of PM-PPDs. The optimal PM-PPDs were achieved using poly(3-hexylthiophene) (P3HT):poly-TPD:PC61BM (80:20:2, wt/wt/wt) as active layers. External quantum efficiency (EQE) values at 620 nm are 3900 and 1250% for PM-PPDs based on P3HT:poly-TPD:PC61BM (80:20:2, wt/wt/wt) and P3HT:PC61BM (100:2, wt/wt) under -10 V applied voltage, respectively. The EQE at 620 nm of optimal PM-PPDs is improved from 650 to 63,000% along with the applied voltage increase from -5 to -20 V. This work provides a new strategy of using transparent polymer with large µh as a regulator for EQE and response speed improvement, as well as the flattened EQE spectral shape of PM-PPDs.

Secondary Grain Growth in Organic-Inorganic Perovskite Films with Ethylamine Hydrochloride Additives for Highly Efficient Solar Cells.

The grain boundaries of perovskite polycrystalline are regarded as a defect region that not only provides carrier recombination sites but also introduces device degradation pathways. Efforts to enlarging the grain size of a perovskite film and reducing its grain boundary are crucial for highly efficient and stable perovskite solar cells (PSCs). Some effective methods that facilitate grain growth are postdeposition thermal annealing and solvent vapor annealing. However, a detailed understanding of grain growth mechanisms in perovskite films is lacking. In this study, perovskite films were prepared by adding ethylamine hydrochloride (EACl) to the precursor solution. This additive strategy promotes a new grain growth mode, secondary grain growth, in perovskite films. Secondary grain growth leads to much larger grains with a high crystallographic orientation. These excellent properties lead to reduced grain boundaries and the densities of boundary defects. The improved film quality results in a prolonged charge-carrier lifetime and a significantly enhanced power conversion efficiency (PCE). Compared with the 18.42% PCE of the control device, the PCE of the device with EACl additives reaches 21.07%.

Correction: Improved fill factor in inverted planar perovskite solar cells with zirconium acetate as the hole-and-ion-blocking layer.

Correction for 'Improved fill factor in inverted planar perovskite solar cells with zirconium acetate as the hole-and-ion-blocking layer' by Xuewen Zhang et al., Phys. Chem. Chem. Phys., 2018, 20, 7395-7400.

Improved fill factor in inverted planar perovskite solar cells with zirconium acetate as the hole-and-ion-blocking layer.

Planar perovskite solar cells (PSCs) have gained great interest due to their low-temperature solution preparation and simple process. In inverted planar PSCs, an additional buffer layer is usually needed on the top of the PCBM electron-transport layer (ETL) to enhance the device performance. In this work, we used a new buffer layer, zirconium acetate (Zr(Ac)4). The inclusion of the Zr(Ac)4 buffer layer leads to the increase of FF from ∼68% to ∼79% and PCE from ∼14% to ∼17% in the planar PSCs. The UPS measurement indicates that the Zr(Ac)4 layer has a low HOMO level of -8.2 eV, indicating that the buffer layer can act as a hole-blocking layer. Surface morphology and surface chemistry investigations reveal that the elements I, MA and Pb can diffuse across the PCBM ETL, damaging the device performance. The covering Zr(Ac)4 molecules fill in the pinholes of the PCBM layer and effectively block the ions/molecules of the perovskite from diffusion across the ETL. The resulting more robust PCBM/Zr(Ac)4 ETL leads to weaker ionic charge accumulation and lower diode leakage current. The double role of hole-and-ion blocking of the Zr(Ac)4 layer explains the improved FF and PCE in the PSCs.

Electron transporting organic materials with an exceptional large scale homeotropic molecular orientation.

An electron transporting anthraquinone derivative demonstrated a stable large-scale homeotropic alignment on an open substrate surface, which substantially improved its charge carrier mobility. The electron mobility (µ(E)) increased by two orders of magnitude from 3.2 × 10(-4) cm(2) V(-1) s(-1) for the film without alignment to 1.2 × 10(-2) cm(2) V(-1) s(-1) for the homeotropically aligned film. A distinct enhancement in the UV absorption spectra of the films around the short wavelength range was observed to be associated with the molecular alignments. These alignments are less sensitive to the substrate under test. The anchoring force of the columnar stacks appears to be related to the nature of the material associated with the strong interaction between the molecules and substrate interface.

A π-Extended Donor-Acceptor-Donor Triphenylene Twin Linked via a Pyrazine Bridge.

ß-Amino triphenylenes can be accessed via palladium catalyzed amination of the corresponding triflate using benzophenone imine. Transformation of amine 6 to benzoyl amide 18 is also straightforward, and its wide mesophase range demonstrates that the new linkage supports columnar liquid crystal formation. Amine 6 also undergoes clean aerobic oxidation to give a new twinned structure linked through an electron-poor pyrazine ring. The new discotic liquid crystal motif contains donor and acceptor fragments and is more oval in shape rather than disk-like. It forms a wide range columnar mesophase. Absorption spectra are strong and broad; emission is also broad and occurs with a Stokes shift of ca. 0.7 eV, indicative of charge-transfer character.

Dynamic interface charge governing the current-voltage hysteresis in perovskite solar cells.

The accumulation of mobile ions causes space charge at interfaces in perovskite solar cells. There is a slow dynamic process of ion redistribution when the bias is changed. The interface charge affects band bending and thus the photocurrent of the solar cells. Consequently the dynamic process of the interface charge governs the current-voltage hysteresis. Very low interface charge density leads to hysteresis-free devices.

Expanded porphyrin-like structures based on twinned triphenylenes.

Triphenylene twins are intriguing structures, and those bridged through their 3,6-positions by dipyrromethene units give a new class of macrocycles that can be viewed as rigid, expanded porphyrin derivatives in which coplanarity is enforced in a formally antiaromatic π system. Somewhat surprisingly, however, macrocyclization leads to significant overall stabilization of the dipyrromethene chromophores.

[Ideal white organic light emitting devices based on doped PFO].

In the present paper, the electroluminescence emission from a doped polymer layer was studied. The blue fluorene PFO was used as the host material and MEH-PPV as the dopant. The spectral characteristics and color stability of the emission on CIE chromaticity diagram were investigated. With the doping ratio of 2.5 Wt%, the device shows turn-on voltage of 3 V, and color coordinates of (0.33, 0.33) at 11 V. The color coordinates of the device was stable with changing voltage in a large range, and located in the ideal white area in the range of 5-20 V voltage.

A mesogenic triphenylene-perylene-triphenylene triad.

A straightforward synthesis of triphenylene-perylene-triphenylene triad structures has been achieved by using versatile triphenylene intermediates bearing a single oxyalkyl amine side chain. Among these, PBITP(10) showed a stable columnar mesophase implying favorably matched core-core separations in the structure. Importantly, the triad can be used as a vehicle for doping columnar triphenylene matrices with functional but incompatible perylene units and a mixture of hexahexyloxytriphenylene matrix doped with 0.1% PBITP(10) is homogeneous and liquid crystalline.

Exploring reversible quenching of fluorescence from a pyrazolo[3,4-b]quinoline derivative by protonation.

Pyrazolo[3,4-b]quinoline derivatives are reported to be highly efficient organic fluorescent materials suitable for applications in light-emitting devices. Although their fluorescence remains stable in organic solvents or in aqueous solution even in the presence of H(2)O, halide salts (LiCl), alkali (NaOH) and weak acid (acetic acid), it suffers an efficient quenching process in the presence of protic acid (HCl) in aqueous or ethanolic solution. This quenching process is accompanied by a change in the UV spectrum, but it is reversible and can be fully recovered. Both steady-state and transient fluorescence spectra of 1-phenyl-3,4-dimethyl-1H-pyrazolo-[3,4-b]quinoline (PAQ5) during quenching are measured and analyzed. It is found that a combined dynamic and static quenching mechanism is responsible for the quenching processes. The ground-state proton-transfer complex [PAQ5H(+)] is responsible for static quenching. It changes linearly with proton concentration [H(+)] with a bimolecular association constant K(S)=1.95 M(-1) controlled by the equilibrium dissociation of HCl in ethanol. A dynamic quenching constant K(D)=22.4 M(-1) is obtained by fitting to the Stern-Volmer equation, with a bimolecular dynamic quenching rate constant k(d)=1.03x10(9) s(-1) M(-1) under ambient conditions. A change in electron distribution is simulated and explains the experiment results.