Universal generative modeling in dual domains for dynamic MRI.

Dynamic magnetic resonance image reconstruction from incomplete k-space data has generated great research interest due to its ability to reduce scan time. Nevertheless, the reconstruction problem remains a thorny issue due to its ill posed nature. Recently, diffusion models, especially score-based generative models, have demonstrated great potential in terms of algorithmic robustness and flexibility of utilization. Moreover, a unified framework through the variance exploding stochastic differential equation is proposed to enable new sampling methods and further extend the capabilities of score-based generative models. Therefore, by taking advantage of the unified framework, we propose a k-space and image dual-domain collaborative universal generative model (DD-UGM), which combines the score-based prior with a low-rank regularization penalty to reconstruct highly under-sampled measurements. More precisely, we extract prior components from both image and k-space domains via a universal generative model and adaptively handle these prior components for faster processing while maintaining good generation quality. Experimental comparisons demonstrate the noise reduction and detail preservation abilities of the proposed method. Moreover, DD-UGM can reconstruct data of different frames by only training a single frame image, which reflects the flexibility of the proposed model.

Rh(III)-catalyzed C-H annulation of sulfoxonium ylides with iodonium ylides towards isocoumarins.

The direct synthesis of isocoumarin skeletons has been realized through the Rh(III)-catalyzed [3 + 3] annulation of sulfoxonium ylides with iodonium carbenes. The synthetic protocol was constructed efficiently with broad functional group tolerance and mild reaction conditions. This reaction can be formally viewed as the result of C-H activation, carbene insertion and nucleophilic addition processes. Furthermore, the further conversions of the product and gram-scale reactions were also demonstrate to support the effectiveness of the synthesis protocol.

Fabrication of hydrophobic NiFe2O4@poly(DVB-LMA) sponge via a Pickering emulsion template method for oil/water separation.

Super-hydrophobic porous absorbents are convenient, low-cost, efficient and environment-friendly materials in the treatment of oil spills. In this work, a simple Pickering emulsion template method was employed to fabricate an interconnected porous poly(DVB-LMA) sponge. A new co-Pickering stabilization system of Span 80 and NiFe2O4 nanoparticles was used to prepare ultra-concentrated internal phase water-in-oil (W/O) emulsions. After further polymerization, the resulting sponges were generated, which exhibited excellent adsorption selectivity due to the super-hydrophobicity and super-lipophilicity. Furthermore, the characterization results indicated that the composites had superior thermal stability, low density, high porosity and a flexible three-dimensional porous structure. Besides, the addition of nickel ferrite nanoparticles provided the materials with extra magnetic operability. High oil adsorption capacity (up to 36.9-84.2 g g-1), high oil retention, fast adsorption rate and superior reusability allowed the materials to be applied in the treatment of oily water.

Copper-Catalyzed Phosphorylation of 2,3-Allenoic Acids and Phosphine Oxide: Access to Phosphorylated Butenolides.

We investigated a novel Cu-catalyzed annulation of 2,3-allenoic acids with diphenylphosphine oxide, leading to the formation of 4-phosphate butenolides in up to 88% yield. The formation of the C-P bond provides new avenues for the functionalization of different furan-2(5H)-ones, with favorable features such as suitable functional group tolerance and mild synthesis conditions.

Direct synthesis of indazole derivatives via Rh(III)-catalyzed C-H activation of phthalazinones and allenes.

A novel Rh(III)-catalyzed annulation of phthalazinones or pyridazinones with various allenes was developed, leading to the formation of indazole derivatives bearing a quaternary carbon in moderate to good yields. The targeted products were synthesized via sequential C-H activation and olefin insertion, followed by ß-hydride elimination and intramolecular cyclization. The synthetic protocol proceeded efficiently with broad functional group tolerance, high atom efficiency and high Z-selectivity. The practicability of this method was proved by synthetic transformation.

Palladium-Catalyzed [2 + 2 + 1] Annulation of Alkyne-Tethered Aryl Iodides with Diaziridinone: Synthesis of 3,4-Fused Tricyclic Indoles.

A novel palladium-catalyzed [2 + 2 + 1] annulation of alkyne-tethered aryl iodides with diaziridinone was developed, leading to the formation of 3,4-fused tricyclic indoles. From a mechanistic standpoint, the formation of fused tricyclic indole scaffolds involved C,C-palladacycles, which were synthesized through the intramolecular reaction of aryl halides and alkynes. The cascade reaction described herein could be carried out with a broad range of substrates and provided various 3,4-fused tricyclic indoles with yields up to 98%.

Controllable synthesis of 3-chloro- and 3,3-dichloro-2-oxindoles via hypervalent iodine-mediated chlorooxidation.

An efficient and controllable protocol for the synthesis of 3-chloro- and 3,3-dichloro-2-oxindoles has been developed via hypervalent iodine-promoted chlorooxidation. By using two equivalents of 1-chloro-1,2-benziodoxol-3-(1H)-one, a wide range of indoles were transformed into 3-chloro-2-oxindoles in DMF/CF3CO2H/H2O at room temperature with good yields. As far as we know, this is the first report on the selective C-2 oxidation and C-3 monochlorination of simple indoles. In addition, three equivalents of the same hypervalent iodine afforded 3,3-dichloro-2-oxindoles in up to 99% yields under optimized conditions (dioxane/H2O, 80 °C). The method features mild reaction conditions, the widespread availability of the substrates, and good functional group tolerance.

Metal-free synthesis of 2,2-disubstituted indolin-3-ones.

A straightforward method for the synthesis of indolin-3-ones bearing a C2-quaternary functionality is reported. A series of 2,2-disubstituted indolin-3-ones were constructed in up to 94% yields in the absence of a metal catalyst. This cross-coupling reaction allows the facile synthesis of 2,2-disubstituted indolin-3-ones from readily available substrates in a short reaction time.

Cobalt(III)-Catalyzed Fast and Solvent-Free C-H Allylation of Indoles Using Mechanochemistry.

Mechanochemical conditions have been applied to a highly efficient cobalt(III)-catalyzed C-H bond activation for the first time. In a subsequent step to the olefin insertion and ß-oxygen elimination, N-pyrimidinylindoles were allylated with vinylethylene carbonates in the absence of organic solvent under high-speed ball-milling condition. As the reaction afforded the desired products in up to 98% yields within a short time, this method constitutes an environmentally friendly and powerful alternative to the common solution-based approaches.

MnFe2O4@C Nanofibers as High-Performance Anode for Sodium-Ion Batteries.

MnFe2O4 nanodots (∼3.3 nm) homogeneously dispersed in porous nitrogen-doped carbon nanofibers (denoted as MFO@C) were prepared by a feasible electrospinning technique. Meanwhile, MFO@C with the character of flexible free-standing membrane was directly used as binder- and current collector-free anode for sodium-ion batteries, exhibiting high electrochemical performance with high-rate capability (305 mA h g(-1) at 10000 mA g(-1) in comparison of 504 mA h g(-1) at 100 mA g(-1)) and ultralong cycling life (ca. 90% capacity retention after 4200 cycles). The Na-storage mechanism was systematically studied, revealing that MnFe2O4 is converted into metallic Mn and Fe after the first discharge (MnFe2O4 + 8Na(+) + 8e(-) → Mn + 2Fe + 4Na2O) and then to MnO and Fe2O3 during the following charge (Mn + 2Fe + 4Na2O → MnO + Fe2O3 + 8Na(+) + 8e(-)). The subsequent cycles occur through reversible redox reactions of MnO + Fe2O3 + 8Na(+) + 8e(-) ↔ Mn + 2Fe + 4Na2O, of which the reduction/oxidation of MnO/Mn takes place at a lower potential than that of Fe2O3/Fe. Furthermore, a soft package sodium-ion full battery with MFO@C anode and Na3V2(PO4)2F3/C cathode was assembled, delivering a stable capacity of ∼400 mA h g(-1) for MFO@C (with 100 cycles at 500 mA g(-1)) and a promising energy density of 77.8 Wh kg(-1) for the whole battery. This is owing to the distinctive structure of very-fine MnFe2O4 nanodots embedded in porous N-doped carbon nanofibers, which effectively improves the utilization rate of active materials, facilitates the transportation of electrons and Na(+) ions, and prevents the particle pulverization/agglomeration upon prolonged cycling.

A Symmetric Co(N5 )2 (H2 O)4 ⋠4 H2 O High-Nitrogen Compound Formed by Cobalt(II) Cation Trapping of a Cyclo-N5- Anion.

The reactions of (N5 )6 (H3 O)3 (NH4 )4 Cl with Co(NO3 )2 ⋅6 H2 O at room temperature yielded Co(N5 )2 (H2 O)4 ⋅4 H2 O as an air-stable orange metal complex. The structure, as determined by single-crystal X-ray diffraction, has two planar cyclo-N5- rings and four bound water molecules symmetrically positioned around the central metal ion. Thermal analysis demonstrated the explosive properties of the material.

Correlated and Multi-frequency Diffusion Modeling for Highly Under-sampled MRI Reconstruction.

Given the obstacle in accentuating the reconstruction accuracy for diagnostically significant tissues, most existing MRI reconstruction methods perform targeted reconstruction of the entire MR image without considering fine details, especially when dealing with highly under-sampled images. Therefore, a considerable volume of efforts has been directed towards surmounting this challenge, as evidenced by the emergence of numerous methods dedicated to preserving high-frequency content as well as fine textural details in the reconstructed image. In this case, exploring the merits associated with each method of mining high-frequency information and formulating a reasonable principle to maximize the joint utilization of these approaches will be a more effective solution to achieve accurate reconstruction. Specifically, this work constructs an innovative principle named Correlated and Multi-frequency Diffusion Model (CM-DM) for highly under-sampled MRI reconstruction. In essence, the rationale underlying the establishment of such principle lies not in assembling arbitrary models, but in pursuing the effective combinations and replacement of components. It also means that the novel principle focuses on forming a correlated and multi-frequency prior through different high-frequency operators in the diffusion process. Moreover, multi-frequency prior further constraints the noise term closer to the target distribution in the frequency domain, thereby making the diffusion process converge faster. Experimental results verify that the proposed method achieved superior reconstruction accuracy, with a notable enhancement of approximately 2dB in PSNR compared to state-of-the-art methods.

Fragmentation pathways of 2-substituted pyrrole derivatives using electrospray ionization ion trap and electrospray ionization quadrupole time-of-flight mass spectrometry.

RATIONALE: Pyrrole derivatives are of considerable importance and are present in a wide range of natural products and used extensively in drug discovery. Fragmentation pathway studies play an important role in the structural identification of pyrrole derivatives. As a part of our ongoing work on heterocycles, fragmentation pathways of 2-substituted pyrrole derivatives were investigated by mass spectrometry (MS). METHODS: Twelve pyrrole derivatives were synthesized and analyzed. Low-resolution fragmentation ions of all the compounds were generated by ion trap mass spectrometry (ITMS(n) ) with an electrospray ionization (ESI) source in positive mode. Hybrid quadrupole time-of-flight mass spectrometry (QTOFMS) was used to determine the elemental compositions of the resultant product ions. RESULTS: The side-chain substituents at the 2-position influence the fragmentation pathways. Typical losses of H2 O, aldehydes and pyrrole moieties from the [M + H](+) ion are observed for the compounds with side chains bearing aromatic groups at the 2-position of the pyrrole. However, losses of H2 O, alcohols and C3 H6 are the main cleavage pathways for compounds 6 and 12 with nonphenyl-substituted side chains at the 2-position. CONCLUSIONS: Typical fragmentation mechanisms of 2-substituted pyrrole derivatives are proposed and elucidated based on the observations of ITMS(n) and QTOFMS spectra. The results showed that the fragmentation pathways were remarkably influenced by the side-chain substituents at the 2-position of pyrrole. This investigation should have value in the structural identification of this series of molecules or compounds with similar structures.

A compressible porous superhydrophobic material constructed by a multi-template high internal phase emulsion method for oil-water separation.

Superhydrophobic porous materials exhibit remarkable stability and exceptional efficacy in combating marine oil spills and containing oily water discharges. This work employed the multi-template high internal phase emulsion method to fabricate a multi-template porous superhydrophobic foam (MTPSF). The materials were characterized through SEM, IR spectroscopy, contact angle measurement, and an electronic universal testing machine. Moreover, the materials' oil-water separation capability, reusability, and compressibility were thoroughly evaluated. The obtained results demonstrate that the material displays a water contact angle of 143° and an oil contact angle of approximately 0°, thus exhibiting superhydrophobic and superoleophilic properties. Consequently, it effectively facilitates the separation of oil slicks and heavy oil underwater. Furthermore, the MTPSF conforms to the second kinetic and Webber-Morris models concerning the oil absorption process. MTPSF exhibits an outstanding oil absorption capacity, ranging from 39.40 to 102.32 g g-1, while showcasing reliable reusability, high recovery efficiency, and excellent compressibility of up to 55%. The above exceptional attributes render the MTPSF highly suitable for oil-water separation applications.

Synthesis of C3-halo substituted bicyclo[1.1.1]pentylamines via halosulfoamidation of [1.1.1]propellane with sodium hypohalites and sulfonamides.

Herein, we report a catalyst-free synthesis of C3-halo substituted bicyclo[1.1.1]pentylamines under mild conditions. The reaction involves the use of sodium hypohalites and sulfonamides to generate N-halosulfonamides in situ, which subsequently undergo radical addition with [1.1.1]propellane to yield the desired products with suitable functional group tolerance.

Photocatalytic Three-Component Synthesis of 3-Heteroarylbicyclo[1.1.1]pentane-1-acetates.

Herein, we report a visible-light-induced three-component reaction involving [1.1.1]propellane, diazoates, and various heterocycles for the synthesis of 3-heteroarylbicyclo[1.1.1]pentane-1-acetates. Throughout this reaction, the radicals generated from diazoate species react with [1.1.1]propellane in an addition reaction to form bicyclo[1.1.1]pentane (BCP) radicals that subsequently react with heterocycles, leading to the formation of 1,3-disubstituted BCP acetates. Notably, this methodology exhibits excellent functional group compatibility, high atom economy, and mild reaction conditions, thus facilitating suitable synthetic access to 1,3-disubstituted BCP acetates.

Visible light-induced gem-difluoroallylation of [1.1.1]propellane to access gem-difluoroallylic bicyclo[1.1.1]pentanes.

Bicyclo[1.1.1]pentanes (BCPs) represent an important compound class often used as linear spacer units to enhance pharmacokinetic profiles in modern drug design. Herein, we report a cascade multicomponent reaction to synthesize gem-difluoroallylic bicyclo[1.1.1]pentanes via visible light-induced defluorinative gem-difluoroallylation of [1.1.1]propellane. In this methodology, sulfonyl radicals generated from sodium arylsulfinates added to [1.1.1]propellane to form BCP radicals were then trapped by α-trifluoromethyl alkenes to form gem-difluoroallylic bicyclo[1.1.1]pentanes. Importantly, our methodology is characterized by mild reaction conditions, wide reactant scope, and suitable functional group tolerance.

Synthesis of Imidized Cyclobutene Derivatives by Strain Release of [1.1.1]Propellane.

Herein, we report the metal-free synthesis of imidized methylene cyclobutane derivatives via a strain-release driven addition reaction of [1.1.1]propellane. Using this strategy, the methylene cyclobutyl cation intermediate generated by protonation of [1.1.1]propellane was found to be trapped by nitriles to form a nitrilium ion intermediate, which subsequently reacted with carboxylic acids to produce imidized methylene cyclobutene derivatives via a Mumm-type rearrangement.

Photoinduced Three-Component Difluoroamidosulfonylation/Bicyclization: A Route to Dihydrobenzofuran Derivatives.

A visible-light-induced photocatalyst-free three-component radical cascade bicyclization has been achieved to obtain diverse difluoroamidosulfonylated dihydrobenzofurans in moderate to good yields. This protocol avoids potential toxicity and the tedious removal procedure for photocatalysts and also features mild reaction conditions and a good functional group tolerance. Moreover, mechanistic investigations reveal the formation of a charge-transfer complex and the involvement of an intramolecular 1,5-hydrogen atom transfer process in this transformation.

Enantioselective Conjugate Addition of Alkenyl Trifluoroborates to Alkenyl-Substituted Benzimidazoles Catalyzed by Chiral Binaphthols.

The enantioselective organocatalytic conjugate alkenylation of ß-substituted alkenyl benzimidazoles afforded ß-stereogenic 2-alkyl benzimidazole derivatives in excellent enantioselectivities. Chiral binaphthols were effective catalysts for promoting the nucleophilic addition of bench-stable alkenyl trifluoroborate salts under mild conditions, expanding their applications by utilizing C=N-containing azaarenes as activating groups. The synthetic utility of this strategy is demonstrated by conversions into several useful enantiomerically enriched benzimidazole building blocks.