Comparative analysis of testicular fusion in Spodoptera litura (cutworm) and Bombyx mori (silkworm): Histological and transcriptomic insights.

Spodoptera litura commonly known as the cutworm, is among the most destructive lepidopteran pests affecting over 120 plants species. The powerful destructive nature of this lepidopteran is attributable to its high reproductive capacity. The testicular fusion that occurs during metamorphosis from larvae to pupa in S.litura positively influences the reproductive success of the offspring. In contrast, Bombyx mori, the silkworm, retains separate testes throughout its life and does not undergo this fusion process. Microscopic examination reveals that during testicular fusion in S.litura, the peritoneal sheath becomes thinner and more translucent, whereas in B.mori, the analogous region thickens. The outer basement membrane in S.litura exhibits fractures, discontinuity, and uneven thickness accompanied by a significant presence of cellular secretions, large cell size, increased vesicles, liquid droplets, and a proliferation of rough endoplasmic reticulum and mitochondria. In contrast, the testicular peritoneal sheath of B.mori at comparable developmental stage exhibits minimal change. Comparative transcriptomic analysis of the testicular peritoneal sheath reveals a substantial difference in gene expression between the two species. The disparity in differential expressed genes (DEGs) is linked to an enrichment of numerous transcription factors, intracellular signaling pathways involving Ca2+ and GTPase, as well as intracellular protein transport and signaling pathways. Meanwhile, structural proteins including actin, chitin-binding proteins, membrane protein fractions, cell adhesion, extracellular matrix proteins are predominantly identified. Moreover, the study highlights the enrichment of endopeptidases, serine proteases, proteolytic enzymes and matrix metalloproteins, which may play a role in the degradation of the outer membrane. Five transcription factors-Slforkhead, Slproline, Slcyclic, Slsilk, and SlD-ETS were identified, and their expression pattern were confirmed by qRT-PCR. they are candidates for participating in the regulation of testicular fusion. Our findings underscore significant morphological and trancriptomic variation in the testicular peritoneal sheath of S.litura compared to the silkworm, with substantial changes at the transcriptomic level coinciding with testicular fusion. The research provides valuable clues for understanding the complex mechanisms underlying this unique phenomenon in insects.

Pushing the limits of the heat of detonation via the construction of polynitro bipyrazole.

The trinitromethyl group is a highly oxidized group that is found as an active functionality in many high-energy-density materials. The most frequently used previous synthetic method for the introduction of the trinitromethyl group is the nitration of heterocyclic compounds containing an acetonyl/ethyl acetate/chloroxime group. Now a novel strategy for constructing a trinitromethyl group (5) via nitration of an ethylene bridged compound, dipyrazolo[1,5-a:5',1'-c]pyrazine (2), is reported. In addition, the other two nitrated products (3 and 4) were obtained under different nitrating conditions. Compound 5 has excellent detonation performance (Dv = 9047 m s-1, P = 35.6 GPa), and a low mechanical sensitivity (IS = 10 J, FS = 216 N), with an especially attractive heat of detonation of 6921 kJ kg-1, which significantly exceeds that of the state-of-the-art explosive CL-20 (Q: 6162 kJ kg-1).

From Tetranitromethane to Gem-Dinitro-Bridged Nitrogen-Rich Heterocyclic Compound: Achieving High Heat of Detonation.

Improving the detonation performance of tetranitromethane (TNM) by introducing energetic moieties is an intriguing area in the field of energetic materials. Incorporation of a mono nitrogen-rich skeleton into TNM usually results in unsatisfactory detonation performance. Now, we reported the design and synthesis of an advanced TNM-like molecule (3) containing nitrogen-rich triazole and nitro-triazinane moieties. In addition, two of its analogues (4 and 5) were also obtained. Taking advantage of the positive heat of formation brought by triazole and triazinane rings and high-density properties donated by many nitro groups, 3 shows promising heat of detonation (Q = 5859 kJ kg-1), which is 2.8 times of TNM and higher than most of its mono ring-modified derivatives (Q: 2076 to 5594 kJ kg-1). The detonation velocity and detonation pressure of 3 (Dv = 8964 m s-1 and P = 35.7 GPa) are competitive with those of RDX (Q = 5763 kJ kg-1, Dv = 8782 m s-1, and P = 34.7 GPa). Structural modification by using triazole and nitro-triazinane rings may be helpful in exploring more TNM derivatives and other types of high-performance explosives.

Dehydrogenative Syntheses of Biazoles via a "Pre-Join" Approach.

The structural motif of biazoles is the predominant substructure of many natural products, pharmaceuticals, and organic materials. Considerable efforts have focused on synthesizing these compounds; however, a limited number of processes have been reported for the efficient formation of biazoles. Herein, we report a "pre-join" approach for the dehydrogenative synthesis of biazoles, which are challenging to prepare using conventional methods. A bench-stable and easily synthesized pyrazine-based group is critical for this transformation. This strategy enables the homocoupling of biazoles and the heterocoupling of two different azoles. Due to the broad substrate scope, this strategy exhibits potential for use in other fields, such as medicine, materials, and natural product chemistry.

The Possible Source of Abnormally High Sodium Content in Low-Salinity Geothermal Water.

The dissolution of sodium-containing minerals in high-temperature geothermal systems can cause Na+ to exceed 400 mg/L with high salinity. But the Na+ of low-salinity geothermal water is mostly less than 100 mg/L in medium-low temperature geothermal systems. However, geothermal water with Na+ up to 325.4 mg/L and total dissolved solids less than 650 mg/L was found in the Huangshadong geothermal field, which is a typical medium-low temperature hydrothermal system in South China. The water chemistry results indicate that thermal groundwater is uniformly HCO3 -Na type with high sodium content (average 240.06 mg/L). All the thermal groundwater and shallow groundwater have the same meteoric origin based on δD and δ18 O. According to water chemical geothermometers and multicomponent mineral equilibrium (MME) method, the reservoir temperature is estimated to be 100 to 130 °C at a maximum depth of 2.43 km. The estimation of the Cl- mixed indicator suggests that geothermal water has mixed with 51% to 72% of shallow groundwater, resulting in the reduction of Na+ content in real geothermal water (Na+ up to 685.2 mg/L). The simulated results of water-rock interactions indicate that mineral dissolution and ion exchange have minor contributions to Na+ enrichment in geothermal water. Hydrochemical simulations and Gibbs diagrams suggest an additional source of high sodium: granite fluid inclusions are fractured into geothermal water at high temperatures. Granite fluid inclusions may only account for 3% to 5% of geothermal water, but they provide the main source of Na+ in geothermal water.

Iridium-Catalyzed Redox-Neutral C2 and C3 Dual C-H Functionalization of Indoles with Nitrones toward 7H-Indolo[2,3-c]quinolines.

An iridium-catalyzed redox-neutral C-2 and C-3 dual C-H functionalization of indoles with nitrones has been developed, furnishing a range of 7H-indolo[2,3-c]quinolines with high efficiency and regioselectivity under mild reaction conditions. Notably, sequential multiple C-H bond cleavage and C-C bond formation constitute the key events of this process, in which nitrone serves as a building block and an oxidant. Distinct from the previous methods toward 7H-indolo[2,3-c]quinolines, this newly developed reaction features readily available substrates, operational simplicity, broad scope, good to high efficiency, and excellent regioselectivity.

Rh(iii)-Catalyzed sequential ortho-C-H oxidative arylation/cyclization of sulfoxonium ylides with quinones toward 2-hydroxy-dibenzo[b,d]pyran-6-ones.

A rhodium(iii)-catalyzed ortho-C-H functionalization of sulfoxonium ylides followed by intramolecular annulation reactions with quinones was described, where the carbonyl in sulfoxonium ylides served as a chelation group. This protocol leads to the efficient formation of 2-hydroxy-6H-benzo[c]chromen-6-one derivatives, proceeding with the cleavage of the C(O)-S bond in sulfoxonium ylides. This protocol featured high chemo-selectivity and functional group tolerance, where sulfoxonium ylides acted as the aroyl sources.

Palladium/copper-catalyzed multicomponent reactions of propargylic amides, halohydrocarbons and CO2 toward functionalized oxazolidine-2,4-diones.

A palladium/copper-catalyzed oxy-carbonation of propargylic amides by halohydrocarbons and CO2 has been developed toward functionalized oxazolidine-2,4-diones. This multi-component reaction (MCR) was triggered by the oxidative addition of RX to Pd(0), followed by the sequential carboxylation of amide and trans-oxopalladation of an electron-deficient triple bond by RPdX species. Finally, the reductive elimination afforded products possessing tetra-substituted vinyl motifs and Pd(0). This protocol features simultaneous formation of three bonds, representing an efficient method for incorporation of CO2 into value-added heterocycles.