L-LOP/LOPP for the treatment of canine gastrointestinal/hepatosplenic lymphoma.

Canine gastrointestinal (GI) and hepatosplenic (HS) high-grade (large cell) lymphomas are uncommon forms of canine lymphomas, with a very poor response to chemotherapy and a very poor prognosis. Currently, there are no established effective chemotherapy protocols for canine GI/HS lymphomas. This case series aimed to retrospectively evaluate the efficacy of lomustine-based protocols L-LOP (L-asparaginase, lomustine, vincristine, and prednisolone) and L-LOPP (with the addition of procarbazine) for treatment of canine GI/HS lymphomas. Medical records of dogs with cytologically or histologically diagnosed lymphoma at CityU Veterinary Medical Centre from 2019 to 2022 were retrospectively reviewed. The L-LOP/LOPP treatment protocol was well tolerated with rare severe adverse events. Median progression-free survival for GI and HS lymphoma was 56 days (range, 10-274 days) and 57 days (range 8-135 days) respectively; while median survival time for GI and HS lymphoma was 93 days (range 10-325 days) and 210 days (range 8-240 days) respectively.

Comparison of the effect of tea shoots during different seasons in Arma chinensis (Hemiptera: Pentatomidae) reared on Ectropis grisescens (Lepidoptera: Geometridae) pupae.

In this study, we compared the growth, development, and fecundity of Arma chinensis (Fallou) reared on pupae of the geometrid Ectropis grisescens Warren fed on tea shoots during different seasons of the year. The raw data on life history were analyzed using the age-stage, 2-sex life table. When reared on spring or winter geometrid pupae, the duration of the immature stage of A. chinensis was significantly longer than in those produced during the summer or autumn. The survival rate of immature A. chinensis reared on autumn geometrid pupae was significantly lower compared to other treatments. Reproductive diapause was observed in adult A. chinensis reared on winter geometrid pupae. The adult preoviposition period (APOP), total preoviposition period (TPOP), and total longevity were significantly longer in A. chinensis reared on winter pupae than in the other treatments. The fecundity of A. chinensis reared on spring geometrid pupae was significantly lower than in the other treatments. The higher intrinsic rate of increase of the A. chinensis reared on summer pupae (r = 0.0966 day-1) and autumn pupae (r = 0.0983 day-1) resulted in higher fecundity, shorter immature duration, and shorter TPOP compared to the winter and spring populations. These findings can be utilized to enhance and sustain biological control of E. grisescens in tea plantations.

Unraveling the Structure-Property-Performance Relationships of Fused-Ring Nonfullerene Acceptors: Toward a C-Shaped ortho-Benzodipyrrole-Based Acceptor for Highly Efficient Organic Photovoltaics.

The high-performance Y6-based nonfullerene acceptors (NFAs) feature a C-shaped A-DA'D-A-type molecular architecture with a central electron-deficient thiadiazole (Tz) A' unit. In this work, we designed and synthesized a new A-D-A-type NFA, termed CB16, having a C-shaped ortho-benzodipyrrole-based skeleton of Y6 but with the Tz unit eliminated. When processed with nonhalogenated xylene without using any additives, the binary PM6:CB16 devices display a remarkable power conversion efficiency (PCE) of 18.32% with a high open-circuit voltage (Voc) of 0.92 V, surpassing the performance of the corresponding Y6-based devices. In contrast, similarly synthesized SB16, featuring an S-shaped para-benzodipyrrole-based skeleton, yields a low PCE of 0.15% due to the strong side-chain aggregation of SB16. The C-shaped A-DNBND-A skeleton in CB16 and the Y6-series NFAs constitutes the essential structural foundation for achieving exceptional device performance. The central Tz moiety or other A' units can be employed to finely adjust intermolecular interactions. The single-crystal X-ray structure reveals that ortho-benzodipyrrole-embedded A-DNBND-A plays an important role in the formation of a 3D elliptical network packing for efficient charge transport. Solution structures of the PM6:NFAs detected by small- and wide-angle X-ray scattering (SWAXS) indicate that removing the Tz unit in the C-shaped skeleton could reduce the self-packing of CB16, thereby enhancing the complexing and networking with PM6 in the spin-coating solution and the subsequent device film. Elucidating the structure-property-performance relationships of A-DA'D-A-type NFAs in this work paves the way for the future development of structurally simplified A-D-A-type NFAs.

Synthesis of 3,3'-(Ethane-1,2-diylidene)bis(indolin-2-one) Promoted by Thermally-activated Electron Transfer and Photoreduction of CO2 to CH4 and CO.

A Sonogashira coupling reaction leads to the formation of a serendipitous product C with the 3,3'-(ethane-1,2-diylidene)bis(indolin-2-one) unit. To our knowledge, our study provides the first example demonstrating that electron transfer between isoindigo and triethylamine can be thermally activated and can be employed in synthesis. The physical properties of C suggest that it possesses decent photo-induced electron-transfer capabilities. Under the illumination of 136 mW cm-2 intensity, C yields ≈2.4 mmol gcat -1 (per gram of catalyst) of CH4 and ≈0.5 mmol gcat -1 of CO in 20 h in the absence of additional metal, co-catalyst, and amine sacrificial agent. The primary kinetic isotope effect suggests that the bond cleavage of water is a rate-determining step in the reduction. Moreover, the CH4 and CO production can be boosted as the illuminance increases. This study demonstrates that organic donor-acceptor conjugated molecules are potential photocatalysts for CO2 reduction.

Naphthalene Diimide-Based Donor-Acceptor-Donor Small Molecules as Metal-Free Organocatalysts for Photocatalytic CO2 Reaction.

The application of organic small molecules as metal-free photocatalysts for light-driven photoreduction of carbon dioxide (CO2) has seldom been explored. This work developed four naphthalene diimide (NDI)-derived donor-acceptor-donor small molecules with different numbers of thiophene units, namely, NDI-2T, NDI-TT, NDI-4T, and NDI-6T, as metal-free photocatalysts to catalyze the reduction of CO2 under irradiation with an air mass 1.5G solar simulator at one-sun intensity. The structure-property relationship was investigated by exploring the effects of the electron-donating ability of the donor units on the optical properties, redox potential, electron-hole distribution, and exciton lifetime. NDI-6T exhibited the most red-shifted absorption, longest exciton lifetime, and strongest electron-hole separation. However, the large upshift in oxidation potential because of the elevated electron-donating ability of the hexathiophene unit significantly reduced the driving force for catalyst regeneration, leading to poor catalytic performance. Alternatively, NDI-4T possessed proper redox potentials, reduced charge-transfer resistance, and excellent photocurrent intensity; therefore, it effectively converted CO2 to a single product of CO in the presence of water as an electron donor without a sacrificial reagent or cocatalyst with a product yield of 168.6 µmol gcat-1 24 h-1, which was considerably higher than those of NDI-TT (111.9 µmol gcat-1 24 h-1), NDI-2T (88.4 µmol gcat-1 24 h-1), and NDI-6T (40.5 µmol gcat-1 24 h-1). This study provides a practical guideline for the molecular design of conjugated organic molecules as promising photocatalysts for CO2 photoreduction.

Chromatic Fulleropyrrolidine as Long-Lived Metal-Free Catalyst for CO2 Photoreduction Reaction.

Conversion of CO2 into carbonaceous fuels with the aid of solar energy has been an important research subject for decades. Owing to their excellent electron-accepting capacities, fullerene derivatives have been extensively used as n-type semiconductors. This work reports that the fulleropyrrolidine functionalized with 4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole, abbreviated as DTBT-C60 , could efficiently catalyze the photoreduction of CO2 to CO. The novel C60 -chromophore dyad structure facilitated better usage of solar light and effective dissociation of excitons. Consequently, the DTBT-C60 exhibited a promising CO yield of 144 µmol gcat -1 under AM1.5G solar illumination for 24 h. Moreover, the isotope experiments demonstrated that water molecules could function as an electron source to reactivate DTBT-C60 . Impressively, DTBT-C60 exhibited an extremely durable catalytic activity for more than one week, facilitating the practical application of photochemical CO2 reaction.

A Fischer-Type Ruthenium Carbene Complex as a Metathesis Catalyst for the Synthesis of Enol Ethers.

The Grubbs G-I or G-II catalyst gives the ruthenium ethoxy carbene complex, which catalyzes ring-opening cross metathesis (ROCM) of a strained cyclic alkene to give a diene where one of the two alkene moieties in the product contains an ethoxy substituent. No polymeric products are detected. Hydrocarbons such as parent norbornene or substituted cyclopropenes can proceed with the reaction smoothly. Tertiary amines, N-alkylimides, esters, and aryl or alkyl bromides remain intact under the reaction conditions. In addition to vinyl ethers, vinylic esters can also be used. The time required to reach a 50% yield of the ROCM product t50 varies from 0.01 to 140 h depending on the strain and nucleophilicity of the double bond. Anchimeric participation of an electron-rich group would result in significant enhancement of the reactivity, and the t50 could be as short as several minutes. A similar substrate without such a neighboring group shows a much slower rate. An exo-norborne derivative reacts much faster than the corresponding endo-isomer. Alkenes with poor nucleophilicity are less favored for the ROCM process, so is less strained cyclooctene.

Microplasma-enabled nanocarbon assembly for the diameter-selective synthesis of colloidal graphene quantum dots.

A microplasma synthesis of diameter-controlled colloidal graphene quantum dots under ambient conditions is demonstrated. The GQD size was controlled by controlling the size of the organosulfate micelles. Experimental and theoretical results suggest that the organosulfate molecules within the micelles undergo nanographene nucleation and growth by solvated electrons during the synthesis.

Aqueous Palladium-Catalyzed Direct Arylation Polymerization of 2-Bromothiophene Derivatives.

Aqueous palladium-catalyzed direct arylation polymerization (DArP) of 2-bromothiophene derivatives 6-(2-(2-bromothiophen-3-yl)ethoxy)hexyl trimethylammonium bromide (T1) and 4-(2-(2-bromothien-3-yl)ethoxy)butylsulfonate (T2) is achieved. The supporting ligand, triphenylphosphine-3,3',3''-trisulfonic acid trisodium salt (m-TPPTs), facilitates DArP of both derivatives; however, its separation from the polymers by dialysis is difficult due to its strong aggregation in water and N,N-dimethylacetamide (DMAc). This is supported by dynamic light scattering, gel permeation chromatography (GPC), and single-crystal X-ray crystallography. Pyrimidine-Pd(OAc)2 is utilized in the DArP of T1 to afford PT1 without ligand contamination. Density functional theory calculations to determine the coordinating capability of the carboxylate/pivalic acid/water to palladium indicate the viability of implementing DArP in water. Finally, polyelectrolyte molecular-weight overestimation by GPC in water is attributed to the polyelectrolyte effect. Aggregation of the conjugated polyelectrolytes leads to a contracted hydrodynamic volume, and the molecular weight and dispersity assessed by GPC in DMAc significantly deviate from the actual values. An objective approach to evaluate the molecular weight for conjugated polyelectrolytes requires further development.

Synthesis of side-chain regioregular and main-chain alternating poly(bichalcogenophene)s and an ABC-type periodic poly(terchalcogenophene).

Three unsymmetrical diiodobichalcogenophenes SSeI2, STeI2, and SeTeI2 and a diiodoterchalcogenophene SSeTeI2 were prepared. Grignard metathesis of SSeI2, STeI2, SeTeI2, and SSeTeI2 occurred regioselectively at the lighter chalcogenophene site because of its relatively lower electron density and less steric bulk. Nickel-catalyzed Kumada catalyst-transfer polycondensation of these Mg species provided a new class of side-chain regioregular and main-chain AB-type alternating poly(bichalcogenophene)s-PSSe, PSTe, and PSeTe-through a chain-growth mechanism. The ring-walking of the Ni catalyst from the lighter to the heavier chalcogenophene facilitated subsequent oxidative addition, thereby suppressing the possibility of chain-transfer or chain-termination. More significantly, the Ni catalyst could walk over the distance of three rings (ca. 1 nm)-from a thiophene unit via a selenophene unit to a tellurophene unit-to form PSSeTe, the first ABC-type regioregular and periodic poly(terchalcogenophene) comprising three different types of 3-hexylchalcogenophenes.

Regio- and stereo-selective [4+4] photodimerization of angular-shaped dialkyltetracenedithiophene.

Angular-shaped dialkyltetracenedithiophenes (aTDTs) undergo [4+4] photodimerization in solution to form a butterfly-shaped skeleton. This reaction proceeds in a regio- and stereo-selective manner, forming only a single planosymmetric syn-[2,2]-daTDT out of six possible products. The photocycloaddition of aTDTs can take place topochemically in the thin-film state while maintaining regio- and stereo-selectivity. Stronger aliphatic dispersion forces and π-π interactions play important roles in forming the eclipsed dimeric complex that leads to the syn-[2,2]-daTDT isomer.

Synthesis of unsymmetrical benzotrichalcogenophenes by N-heterocyclic carbene-palladium-catalyzed intramolecular direct C3-arylation of chalcogenophenes.

A series of new unsymmetrical benzotrichalcogenophenes (BTCs) were synthesized by the Pd-N-heterocyclic carbene catalyzed intramolecular C3-arylation of furan, thiophene, selenophene and tellurophene units. This is the first time that a C3-direct arylation of selenophene and tellurophene moieties has ever been demonstrated.

Stacking Principles on π- and Lamellar Stacking for Organic Semiconductors Evaluated by Energy Decomposition Analysis.

Two stacking manners, that is, π- and lamellar stacking, are generally found for organic semiconductors, in which the π-stacking occurs between conjugated groups and the lamellar stacking refers to the separation of the conjugated and aliphatic moieties. The stacking principles are yet not well-defined. In this work, extended transition state-natural orbitals for chemical valence (ETS-NOCV), an energy decomposition analysis, is utilized to examine the π- and lamellar stacking for a series of naphthalenetetracarboxylic diimide (R-NDI) crystals. The crucial role of dispersion is validated. The perception that π-stacking is merely determined by the conjugated moiety is challenged. The stacking principles are associated with the closest packing model. Nanoscopic phase separation of conjugated and aliphatic moieties and the formation of lamellar and herringbone motifs in the R-NDIs can thus be clarified. Moreover, the interactions between NDI and the alkyl chain are investigated, revealing that the interactions can be significant, being contradictory to the conventional point of view. Along with R-NDIs, additional organic crystals consisting of various conjugated functionalities and substituents are also investigated by ETS-NOCV. The sampling scope is up to 108 conjugated molecules. The dominant role of dispersion force irrespective of the variation in the conjugated moieties and substituents is further confirmed. It is envisaged that the established principles are applicable to other organic semiconductors. The perspective toward the π- and lamellar stacking might be modified, paving the way for ultimate morphological control.

Bispentafluorophenyl-Containing Additive: Enhancing Efficiency and Morphological Stability of Polymer Solar Cells via Hand-Grabbing-Like Supramolecular Pentafluorophenyl-Fullerene Interactions.

A new class of additive materials bis(pentafluorophenyl) diesters (BFEs) where the two pentafluorophenyl (C6F5) moieties are attached at the both ends of a linear aliphatic chain with tunable tether lengths (BF5, BF7, and BF13) were designed and synthesized. In the presence of BF7 to restrict the migration of fullerene by hand-grabbing-like supramolecular interactions induced between the C6F5 groups and the surface of fullerene, the P3HT:PC61BM:BF7 device showed stable device characteristics after thermal heating at 150 °C for 25 h. The morphologies of the active layers were systematically investigated by optical microscopy, grazing-incidence small-angle X-ray scattering (GISAXS), and atomic force microscopy. The tether length between the two C6F5 groups plays a pivotal role in controlling the intermolecular attractions. BF13 with a long and flexible tether might form a BF13-fullerene sandwich complex that fails to prevent fullerene's movement and aggregation, while BF5 with too short tether length decreases the possibility of interactions between the C6F5 groups and the fullerenes. BF7 with the optimal tether length has the best ability to stabilize the morphology. In sharp contrast, the nonfluorinated BP7 analogue without C6F5-C60 physical interactions does not have the capability of morphological stabilization, unambiguously revealing the necessity of the C6F5 group. Most importantly, the function of BF7 can be also applied to the high-performance PffBT4BT-2OD:PC71BM system, which exhibited an original PCE of 8.80%. After thermal heating at 85 °C for 200 h, the efficiency of the PffBT4BT-2OD:PC71BM:BF7 device only decreased slightly to 7.73%, maintaining 88% of its original efficiency. To the best of our knowledge, this is the first time that the thermal-driven morphological evolution of the high-performance PffBT4BT-2OD polymer has been investigated, and its morphological stability in the inverted device can be successfully preserved by the incorporation of BF7. This research also demonstrates that BF7 is not only effective with PC61BM but also to PC71BM.

Side-chain modulation of dithienofluorene-based copolymers to achieve high field-effect mobilities.

A ladder-type dithieno[3,2-b:6,7-b']fluorene (DTF), where the central fluorene is fused with two outer thiophene rings at its 2,3- and 6,7-junctions, is developed. The pentacyclic DTF monomers were polymerized with dithienodiketopyrrolopyrrole (DPP) acceptors to afford three alternating donor-acceptor copolymers PDTFDPP16, PDTFDPP20, and PDTFDPP32 incorporating different aliphatic side chains (R1 group at DTF; R2 group at the DPP moieties). The side-chain variations in the polymers play a significant role in determining not only the intrinsic molecular properties but also the intermolecular packing. As evidenced by the 2-dimensional GIXS measurements, PDTFDPP16 with octyl (R1) and 2-ethylhexyl (R2) side chains tends to align in an edge-on π-stacking orientation, whereas PDTFDPP20 using 2-butyloctyl (R1) and 2-ethylhexyl (R2) adopts a predominately face-on orientation. PDTFDPP32 with the bulkiest 2-butyloctyl (R1) and 2-octyldodecyl (R2) side chains shows a less ordered amorphous character. The OFET device using PDTFDPP20 with a face-on orientation determined by GIXS measurements achieved a high hole-mobility of up to 5 cm2 V-1 s-1. The high rigidity and coplanarity of the DTF motifs play an important role in facilitating intramolecular 1-dimensional charge transport within the polymer backbones. The implementation of main-chain coplanarity and side-chain engineering strategies in this research provides in-depth insights into structure-property relationships for guiding development of high-mobility OFET polymers.

Synthesis and Isomeric Effects of Ladder-Type Alkylated Terbenzodithiophene Derivatives.

A new class of heptacyclic ladder-type terbenzodithiophene (TBDT) structures merging three fused benzodithophenes was developed. Two TBDT conjugated isomers, named as syn-TBDT and anti-TBDT, where the two thienyl rings in the outmost BDT units are in the syn- and anti-fashion, are designed. Two decyl groups are introduced to their 6,13 and 7,14-positions to form four isomeric 6,13-syn-TBDT, 7,14-syn-TBDT, 6,13-anti-TBDT, and 7,14-anti-TBDT structures which are constructed by the DBU-induced 6-benzannulation involving propargyl-allenyl isomerization of the dieneyne moieties in the corresponding precursors followed by 6π-electrocyclization/aromatization, while isomeric TD-syn-TBDT and TD-anti-TBDT with four decyl groups substituted at 6,7,13,14-positions are synthesized via palladium-catalyzed dialkylacetylene insertion/C-H arylation of the corresponding iodobiaryl precursors. The intrinsic properties can be modulated by molecular manipulation of the main-chain and side-chain isomeric structures. anti-TBDT derivatives exhibit higher melting points, larger bandgaps, stronger intermolecular interactions, and higher mobility than the corresponding syn-TBDT analogues. These molecules can be further utilized as building blocks to make various TBDT-based materials for optoelectronic applications.

Synthesis and Molecular Properties of Two Isomeric Dialkylated Tetrathienonaphthalenes.

Isomeric 2,8-distannyl 5,11-didodecyl αß-TTN (1, tetrathienonaphthalene = TTN) and 2,8-didodecyl 5,11-distannyl αß-TTN (2) have been designed and successfully synthesized. The naphthalene core structures in αß-TTNs were constructed by a systematic protocol using PtCl2-catalyzed cyclization followed by oxidative Scholl annulation in good yields. Compared to the one-dimensional naphthodithiophene derivatives, the two-dimensional αß-TTN molecules showed good solubility, extended conjugation, strong absorptivity, and highly coplanar structures. Compounds 1 and 2 were polymerized with a 5,5'-dibromo-2,2'-bithiophene-based monomer to afford 2,8-αß-PTTNTT and 5,11-αß-PTTNTT copolymers. 2,8-αß-PTTNTT with the α-aNDT moiety in the main chain exhibited a higher hole mobility of 1.26 × 10(-2) cm(2) V(-1) s(-1).

One-pot selective synthesis of a fullerene bisadduct for organic solar cell applications.

A single isomer of fullerene bisadduct, PC61PF, was obtained from commercially available fullerene derivative, PC61BM, in one pot over two steps. The tether-directed remote functionalization approach provided a very simple and fast method to produce a single isomer of fullerene bisadduct with good yield and easy purification. Bulk heterojunction organic solar cells containing the bisadduct was fabricated and tested.

Synthesis and molecular properties of tricyclic biselenophene-based derivatives with nitrogen, silicon, germanium, vinylidene, and ethylene bridges.

A new class of biselenophene-based materials including an sp(3)-silicon-bridged diselenosilole (DSS), an sp(3)-germanium-bridged diselenogermole (DSG), and an sp(3)-nitrogen-bridged diselenopyrrole (DSP) as well as an sp(2)-vinylidene-bridged dicyanodiselenofulvene (CDSF), a diacetylenediselenofulvene (ADSF), and a dioctylethylene-bridged benzodiselenophene (BDS) have been successfully synthesized and characterized. The bridging moieties play an important role in determining the optical and electrochemical properties. The six brominated derivatives are ready to construct various biselenophene-based conjugated materials with tunable properties for organic photovoltaics and field effect transistors.

Synthesis and supramolecular assembly of pentacyclic dithienofluorene and diselenophenofluorene derivatives.

2,7-Diiodo-3,6-dibromofluorene and 2,7-dichloro-3,6-dibromofluorene have been successfully synthesized. The two key intermediates enable us to implement a regioselective Sonogashira reaction followed by intramolecular thiolate/acetylene cyclization, forming two regiospecific pentacyclic dithieno[2,3-b:7,6-b']fluorene (2,7-DTF) and dithieno[3,2-b:6,7-b']fluorene (3,6-DTF) isomeric molecules, respectively. By using a similar strategy, selenophene-based diselenopheno[2,3-b:7,6-b']fluorene (2,7-DSF) as well as diselenopheno[3,2-b:6,7-b']fluorene (3,6-DSF) were also prepared. The isomeric and sulfur/selenium effects determine the optical, electrochemical, and orbital properties. X-ray crystallography revealed that 2,7-DTF and 3,6-DTF molecules assemble into supramolecular helical structures.