Tailoring the Molecular Planarity of Perylene Diimide-Based Third Component toward Efficient Ternary Organic Solar Cells.

Incorporating a third component into binary organic solar cells (b-OSCs) has provided a potential platform to boost power conversion efficiency (PCEs). However, gaining control over the non-equilibrium blend morphology via the molecular design of the perylene diimide (PDI)-based third component toward efficient ternary organic solar cells (t-OSCs) still remains challenging. Herein, two novel PDI derivatives are developed with tailored molecular planarity, namely ufBTz-2PDI and fBTz-2PDI, as the third component for t-OSCs. Notably, after performing a cyclization reaction, the twisted ufBTz-2PDI with an amorphous character transferred to the highly planar fBTz-2PDI followed by a semi-crystalline character. When incorporating the semi-crystalline fBTz-2PDI into the D18:L8-BO system, the resultant t-OSC achieved an impressive PCE of 18.56%, surpassing the 17.88% attained in b-OSCs. In comparison, the addition of amorphous ufBTz-2PDI into the binary system facilitates additional charge trap sites and results in a deteriorative PCE of 14.37%. Additionally, The third component fBTz-2PDI possesses a good generality in optimizing the PCEs of several b-OSCs systems are demonstrated. The results not only provided a novel A-DA'D-A motif for further designing efficient third component but also demonstrated the crucial role of modulated crystallinity of the PDI-based third component in optimizing PCEs of t-OSCs.

Anion-π Interaction Powered Perrhenate Recognition and Extraction in Aqueous Media.

Selective anion recognition and extraction in aqueous media is a challenging research topic, and the anion-π interaction is an undetermined solution for the development of anion sorbent materials with better affinity and selectivity. Here, noncovalent anion-π interaction was introduced as the driving force for this purpose. A cage-based 2D cationic metal-organic framework, IPM-21, is featured with porous channels formed by complementary V-shape electron-deficient cavities. This 3D rhombic electron-deficient cavity can bind two anions with the clipped π-acidic surfaces, exhibiting much higher affinity toward ReO4- due to the strong complementary effect. This cavity was forced to expand its opening size to seamlessly adopt the ReO4- anion with a large volume. Experimental results found that the binding energy of IPM-21 with ReO4- is around 2.3 kJ/mol higher than that with ClO4-. Parts per million levels of the ReO4- anion in aqueous media can be effectively extracted by IPM-21 with a removal up to 99%, even with mixed competing anions. IPM-21 can be easily recycled and reused by treatment with high concentration aqueous NaClO4. Due to the extremely low interlamellar interaction, the IPM-21 crystal exhibited enhanced ReO4- extraction performance with the recycling times due to self-exfoliation; as a result, ultrathin IPM-21 nanosheets with large lateral sizes were produced in this process.

Fe2O3-Promoted Intermolecular Chlorotrifluoromethylthiolation of Alkenes.

A simple, convenient method for intermolecular chlorotrifluoromethylthiolation of alkenes by using a low-cost and more abundant iron catalyst has been developed. This protocol provides a straightforward way to synthesize a variety of useful SCF3-containing chlorides from a wide range of alkenes, including electron-deficient, aromatic, and unactivated alkenes. Mechanistic studies indicate that this is a free radical transformation, and the stronger electrophilic trifluoromethylthiolating reagent CF3SCl was generated in situ under the employed conditions. The synthetic applications of this approach were also explored by a variety of synthetically useful transformations.

Synthesis, Characterization, and Magnetic Resonance Evaluation of Polyglycerol-Functionalized Detonation Nanodiamond Conjugated with Gadolinium(III) Complex.

A nanodiamond-polyglycerol-gadolinium(ll) conjugate has been designed and prepared as novel nanodiamond-based magnetic resonance (MR) contrast agent dispersible in physiological media. Detonation nanodiamond (dND) was first grafted with polyglycerol (PG) through ring-opening polymerization of glycidol to impart dispersibility to dND in physiological media. Since the hydroxyl group in PG serves as a scaffold for further surface functionalization, diethylenetriaminepentaacetic acid (DTPA) was immobilized on the surface of dND-PG through multistep organic transformations and Gd(III) ion was complexed in the last step. The resulting dND-PG-Gd(III) exhibited good dispersibility (> 4.5 mg/mL) and stability (> 3 months) in phosphate buffered saline (PBS). In vitro MR evaluation indicates that water proton T1 relaxivity or r1 of dND-PG-Gd(III) in aqueous solutions is larger than that of Magnevist® and the difference in the relaxivity becomes larger under weaker magnetic fields. The good dispersibility together with relatively high T1 relaxivity makes dND-PG-Gd(III) a promising contrast agent for in vivo MR imaging.

Polyglycerol-functionalized nanodiamond as a platform for gene delivery: Derivatization, characterization, and hybridization with DNA.

A gene vector consisting of nanodiamond, polyglycerol, and basic polypeptide (ND-PG-BPP) has been designed, synthesized, and characterized. The ND-PG-BPP was synthesized by PG functionalization of ND through ring-opening polymerization of glycidol on the ND surface, multistep organic transformations (-OH → -OTs (tosylate) → -N3) in the PG layer, and click conjugation of the basic polypeptides (Arg8, Lys8 or His8) terminated with propargyl glycine. The ND-PG-BPP exhibited good dispersibility in water (>1.0 mg/mL) and positive zeta potential ranging from +14.2 mV to +44.1 mV at neutral pH in Milli-Q water. It was confirmed by gel retardation assay that ND-PG-Arg8 and ND-PG-Lys8 with higher zeta potential hybridized with plasmid DNA (pDNA) through electrostatic attraction, making them promising as nonviral vectors for gene delivery.

The role of gut microbiota and the gut-lung axis in sepsis: A case study of a pregnant woman with severe rickettsial pneumonia and septic shock complicated by MODS.

Key Clinical Message: In this case report, we describe the successful management of severe scrub typhus with pneumonia, sepsis, and multiple organ dysfunction in a pregnant woman. Despite initial challenges, the patient responded favorably to fecal microbiota transplantation and oral fecal microbiota capsule therapy. Abstract: Scrub typhus, caused by Orientia tsutsugamushi, can lead to severe multiorgan dysfunction and carries a mortality rate of up to 70% if not treated properly. In this report, we present the case of a 27-year-old pregnant woman at 18 + 6 weeks gestation whose symptoms worsened 15 days after onset and progressed to severe pneumonia with sepsis and multiple organ dysfunction syndrome. After the pathogen was confirmed by next-generation sequencing analysis of bronchoalveolar-lavage fluid and blood samples, the patient's treatment was switched to antiinfective chloramphenicol. The patient also underwent uterine evacuation due to a miscarriage. Extracorporeal membrane oxygenation was discontinued once the pulmonary infection significantly improved. Subsequently, the patient had recurrent diarrhea, abdominal distension, and difficulty eating. The antibiotic regimen was adjusted according to the drug sensitivity, but the diarrhea and abdominal distension still did not improve. Following a comprehensive multidisciplinary risk assessment, we initiated fecal microbiota transplantation and oral fecal microbiota capsule therapy. As a result, the patient's condition was effectively managed, and they were gradually discharged. Fecal microbiota transplantation may be a safe and effective treatment for severe pneumonia and shock in pregnant women. This has significant implications for maternal health. However, further clinical cases are required to observe its long-term effectiveness.

Donor-Acceptor Copolymer with a Linear Backbone Induced Ordered and Robust Doping Morphology for Efficient and Stable Organic Electrochemical Devices.

Donor (D)-acceptor (A) copolymer-based organic mixed ionic-electronic conductors (OMIECs) exhibit intrinsic environmental stability for they have tailored energy levels. However, their figure-of-merit (µC*) is still falling behind the D-D polymers because of morphology deterioration during the electrochemical doping process. Herein, we developed two D-A copolymers with precisely regulated backbone curvature, namely PTBT-P and PTTBT-P. Compared to the curved PTBT-P and previously reported copolymers, PTTBT-P better keeps its backbone linear, leading to a long-range ordered doping morphology, which is revealed by the in operando X-ray technique. This optimized doping morphology enables a significantly improved operando charge mobility (µ) of 2.44 cm2 V-1 s-1 and a µC* value of 342 F cm-1 V-1 s-1, one of the highest values in D-A copolymer based on OECTs. Besides, we fabricated PTTBT-P-based electrochemical random-access memories and achieved ideal and robust conductance modulation. This study highlights the critical role of backbone curvature control in the optimization of doping morphology for efficient and robust organic electrochemical devices.

Alicyclic polyimides with large band gaps exhibit superior high-temperature capacitive energy storage.

Flexible polymer dielectrics for capacitive energy storage that can function well at elevated temperatures are increasingly in demand for continuously advancing and miniaturizing electrical devices. However, traditional high-resistance polymer dielectrics composed of aromatic backbones have a compromised band gap (Eg) and hence suffer from low breakdown strength and a huge loss at high temperatures. Here, based on the density functional theory (DFT) calculations, rigid and non-coplanar alicyclic segments are introduced into the polyimide backbone to overcome the incompatibility of a high glass transition temperature (Tg) and large Eg. Thanks to the large optical Eg (∼4.6 eV) and high Tg (∼277 °C), the all-alicyclic polyimide at 200 °C delivers a maximum discharge energy density (Ue) of 5.01 J cm-3 with a charge-discharge efficiency (η) of 78.1% at 600 MV m-1, and a record Ue of 2.55 J cm-3 at η = 90%, which is 10-fold larger than that of the state-of-art commercial polyetherimides (PEIs). In addition, compared with aromatic polyimides, the all-alicyclic polyimide possesses a better self-clearing characteristic due to a smaller ratio of carbon to hydrogen and oxygen, which facilitates its long-term reliability in practical applications.

Diastereoselective synthesis of chroman bearing spirobenzofuranone scaffolds via oxa-Michael/1,6-conjugated addition of para-quinone methides with benzofuranone-type olefins.

A simple and convenient cyclization of ortho-hydroxyphenyl-substituted para-quinone methides with benzofuran-2-one type active olefins via oxa-Michael/1,6-conjugated addition has been developed, which afforded an easy access to enriched functionalized chroman-spirobenzofuran-2-one scaffolds with good to excellent yields (up to 90%) and diastereoselectivities (up to >19 : 1 dr). This reaction provided an efficient method for constructing desired spirocyclic compounds combining both well-known heterocyclic pharmacophores chroman and benzofuran-2-one.

Polyimide Nanodielectrics Doped with Ultralow Content of MgO Nanoparticles for High-Temperature Energy Storage.

Advanced polymer dielectrics with high energy density at elevated temperatures are highly desired to meet the requirements of modern electronic and electrical systems under harsh conditions. Herein, we report a novel polyimide/magnesium oxide (PI/MgO) nanodielectric that exhibits high energy storage density (Ue) and charge-discharge efficiency (η) along with excellent cycling stability at elevated temperatures. Benefiting from the large bandgap of MgO and the extended interchain spacing of PI, the composite films can simultaneously achieve high dielectric constant and high breakdown strength, leading to enhanced energy storage density. The nanocomposite film doped with 0.1 vol% MgO can achieve a maximum Ue of 2.6 J cm-3 and a η of 89% at 450 MV m-1 and 150 °C, which is three times that of the PI film under the same conditions. In addition, embedding ultralow content of inorganic fillers can avoid aggregation and facilitate its large-scale production. This work may provide a new paradigm for exploring polymer nanocomposites with excellent energy storage performance at high temperatures and under a high electric field.

Regulating the Aggregation of Unfused Non-Fullerene Acceptors via Molecular Engineering towards Efficient Polymer Solar Cells.

Tuning molecular aggregation via structure design to manipulate the film morphology still remains as a challenge for polymer solar cells based on unfused non-fullerene acceptors (UF-NFAs). Herein, a strategy was developed to modulate the aggregation patterns of UF-NFAs by systematically varying the π-bridge (D) unit and central core (A') unit in A-D-A'-D-A framework (A and D refer to electron-withdrawing and electron-donating moieties, respectively). Specifically, the quantified contents of H- or J-aggregation and crystallite disorder of three UF-NFAs (BDIC2F, BCIC2F, and TCIC2F) were analyzed via UV/Vis spectrometry and grazing incidence X-ray scattering. The results showed that the H-aggregate-dominated BCIC2F with less crystallite disorder exhibited a more favorable blend morphology with polymer donor PBDB-T (poly[(2,6-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene)-co-(1,3-di(5-thiophene-2-yl)-5,7-bis(2-ethylhexyl)benzo[1,2-c:4,5-c']dithiophene-4,8-dione)]) relative the other two UF-NFAs, resulting in improved exciton dissociation and charge tranport. Consequently, photovoltaic devices based on BCIC2F delivered a promising power conversion efficiency of 12.4 % with an exceptionally high short-circuit current density of 22.1 mA cm-2 .

Chlorotrifluoromethylthiolation of Sulfur Ylides for the Formation of Tetrasubstituted Trifluoromethylthiolated Alkenes.

Tetrasubstituted trifluoromethylthiolated alkenes can be accomplished directly through the chlorotrifluoromethylthiolation of sulfur ylides utilizing nucleophilic halide reagent and electrophilic SCF3 reagent. This cascade reaction is mild, highly practical, easy to manipulate, uses catalyst-free conditions, and demonstrates a wide substrate range with excellent functional group tolerance, furnishing E-selective products in good to high yields. The synthetic utility of this approach is documented through gram-scale preparation and late-stage modification of pharmaceutically relevant compounds, making it suitable for drug discovery.

Practical and regioselective halo-trifluoromethylthiolation of sulfur ylides.

A H2O mediated practical and highly regioselective chloro- and bromo-trifluoromethylthiolation of sulfur ylides is reported using a difunctionalization strategy. In the reaction sequence, sulfur ylides presumably react with an electrophilic trifluoromethylthiolating reagent to generate an α-SCF3 substituted sulfonium salt intermediate, which then undergoes a substitution with nucleophilic halogens.

Toward Efficient All-Polymer Solar Cells via Halogenation on Polymer Acceptors.

Although halogenation has been widely regarded as an effective approach to adjust the properties of organic semiconductors, systematic investigation on the comparison of nonhalogenated and halogenated polymer acceptors only received minor attention in all-polymer solar cell (all-PSC) community. Herein, we report three IDIC-based narrow band gap polymer acceptors, PIDIC2T, PIDIC2T2F, and PIDIC2T2Cl, which are composed of IDIC-C16 building blocks as acceptor units, linking pristine bithiophene, fluorinated bithiophene, or chlorinated bithiophene as donor units. Although these three polymer acceptors exhibit nearly identical lowest unoccupied molecular orbital (LUMO) levels of ca. -3.87 eV with a similar optical band gap of ca. 1.54 eV, we found that different halogen species significantly affect the electron mobility and thin-film morphology of the polymer acceptors. All-PSCs were fabricated by pairing three polymer acceptors with a PBDB-T polymer donor, while PIDIC2T2Cl delivered a highest power conversion efficiency (PCE) of 5.34% due to its favorable bulk morphology with smaller root-mean-square (rms) roughness values, which induce the relatively more balanced charge carrier mobilities. By blending the fluorinated analogue of PBDB-T, PM6, further improved VOC, JSC, and fill factor (FF) of devices were achieved (5.46% for PM6:PIDIC2T, 4.96% for PM6:PIDIC2T2F, 7.11% for PM6:PIDIC2T2Cl), which can be due to the synergistic effect of the deeper highest occupied molecular orbital (HOMO) energy level of PM6, enhanced crystallinity, and more matched charge transport. This systematic study provides an insight into the influence of halogenation (fluorination and chlorination) on the optoelectrical properties of n-type organic semiconductors and demonstrates an efficient strategy that the design guideline for polymer acceptors can be enriched by backbone halogenation to further develop high-performance all-PSCs.

3-(2-Bromo-phen-yl)-N-phenyl-oxirane-2-carboxamide.

In the mol-ecule of the title compound, C(15)H(12)BrNO(2), the two benzene rings adopt a syn configuration with respect to the ep-oxy ring; the dihedral angles between the ep-oxy ring and the two benzene rings are 59.90 (13) and 68.01 (12)°. Inter-molecular N-H⋯O and C-H⋯O hydrogen bonding is present in the crystal structure.

3-(3-Bromo-phen-yl)-N-phenyl-oxirane-2-carboxamide.

There are two independent mol-ecules in the asymmetric unit of the title compound, C(15)H(12)BrNO(2). In both mol-ecules, the two benzene rings adopt a cis configuration with respect to the ep-oxy ring. In one mol-ecule, the ep-oxy ring makes dihedral angles of 60.5 (2) and 77.92 (19)° with the two benzene rings; in the other mol-ecule, the values are 61.0 (2) and 81.43 (19)°. Inter-molecular N-H⋯O and C-H⋯O hydrogen bonding is present in the crystal structure.

Efficient delivery of chlorin e6 into ovarian cancer cells with octalysine conjugated superparamagnetic iron oxide nanoparticles for effective photodynamic therapy.

In cancer treatment, efficient delivery of active anticancer drugs into cancer cells is highly desirable for maximizing therapeutic effects and alleviating side effects. In this work, a nanocarrier consisting of an Fe3O4 core, a polyglycerol coating, and an octalysine functionality (SPION-PG-Lys8) has been designed, synthesized and used to deliver a photosensitizer, chlorin e6 (Ce6), into cancer cells for photodynamic therapy (PDT) of cancer cells. SPION-PG-Lys8 is colloidally stable in various aqueous solutions, showing a high positive zeta potential of 47.2 ± 6.9 mV in pure water. In vitro characterization reveals that SPION-PG-Lys8 is efficiently taken up by SKOV3 ovarian cancer cells, exhibiting low cytotoxicity, and suppressed autophagy compared to bare SPIONs. Negatively charged Ce6 is thus loaded on the SPION-PG-Lys8 through electrostatic attraction to yield a SPION-PG-Lys8/Ce6 nanocomplex with a positive zeta potential of 22.4 ± 4.3 mV. SPION-PG-Lys8/Ce6 is more easily taken up by the cells than free Ce6, and surprisingly, the internalized SPION-PG-Lys8/Ce6 is found to be enriched in the mitochondria. SPION-PG-Lys8/Ce6 exhibits almost no cytotoxicity under dark conditions, but strong photocytotoxicity due to the light-triggered production of reactive oxygen species (ROS) destroying the mitochondria. Taken together, our results highlight the great potential of SPION-PG-Lys8 as an efficient carrier of Ce6 for photodynamic cancer therapy.

Direct Fabrication of the Graphene-Based Composite for Cancer Phototherapy through Graphite Exfoliation with a Photosensitizer.

We report on the application of pristine graphene as a drug carrier for phototherapy (PT). The loading of a photosensitizer, chlorin e6 (Ce6), was achieved simply by sonication of Ce6 and graphite in an aqueous solution. During the loading process, graphite was gradually exfoliated to graphene to give its composite with Ce6 (G-Ce6). This one-step approach is considered to be superior to the graphene oxide (GO)-based composites, which required pretreatment of graphite by strong oxidation. Additionally, the directly exfoliated graphene ensured a high drug loading capacity, 160 wt %, which is about 10 times larger than that of the functionalized GO. Furthermore, the Ce6 concentration for killing cells by G-Ce6 is 6-75 times less than that of the other Ce6 composites including GO-Ce6.

High-Efficiency Small Molecule-Based Bulk-Heterojunction Solar Cells Enhanced by Additive Annealing.

Solvent additive processing is important in optimizing an active layer's morphology and thus improving the performance of organic solar cells (OSCs). In this study, we find that how 1,8-diiodooctane (DIO) additive is removed plays a critical role in determining the film morphology of the bulk heterojunction OSCs in inverted structure based on a porphyrin small molecule. Different from the cases reported for polymer-based OSCs in conventional structures, the inverted OSCs upon the quick removal of the additive either by quick vacuuming or methanol washing exhibit poorer performance. In contrast, the devices after keeping the active layers in ambient pressure with additive dwelling for about 1 h (namely, additive annealing) show an enhanced power conversion efficiency up to 7.78% with a large short circuit current of 19.25 mA/cm(2), which are among the best in small molecule-based solar cells. The detailed morphology analyses using UV-vis absorption spectroscopy, grazing incidence X-ray diffraction, resonant soft X-ray scattering, and atomic force microscopy demonstrate that the active layer shows smaller-sized phase separation but improved structure order upon additive annealing. On the contrary, the quick removal of the additive either by quick vacuuming or methanol washing keeps the active layers in an earlier stage of large scaled phase separation.

[Status of perfluorochemicals in adult serum and umbilical blood in Shenyang].

OBJECTIVE: To study the status of perfluorooctane sulfonate (PFOS), and Perfluorooctanoic acid (FOA) pollution in serum and umbilical blood among general people in Shenyang area. METHODS: Concentration of PFOS and PFOA in adult serum and umbilical blood samples was measured by means of liquid phase chromatography/mass spectrograph selective iron monitoring (PFOS: m/z = 499, PFOA: m/z = 413). RESULTS: It was showed that geometric mean of serum concentration of PFOS of male was 40.73microg/L and that of female was 45.46microg/L, PFOA is 11.53microg/L and 8.97microg/L. Geometric mean concentration of PFOS and PFOA in umbilical blood was 2.214microg/L and 0.264microg/L. There was no correlativity between concentration of PFOS, PFOA and age in adult serum and umbilical blood. CONCLUSION: It was suggested that there was PFOS contamination in common group in Shenyang. Also, fetus was exposed in PFOS and PFOA during its embryonic period. There were also PFOS and PFOA pollution in human umbilical blood samples.