Ion pair assisted micro matrix solid phase dispersion extraction of alkaloids from medical plant

A novel micro matrix solid phase dispersion method was successfully used for the extraction of quaternary alkaloids in Phellodendri chinensis cortex. The elution of target compounds was accomplished with sodium hexanesulfonate as the eluent solvent. A neutral ion pair was formed between ion-pairing reagent and positively charged alkaloids in this process, which was beneficial for selectively extraction of polar alkaloids. Several parameters were optimized and the optimal conditions were listed as follows: silica gel as the sorbent, silica to sample mass ratio of 1:1, the grinding time of 1 min. The exhaustive elution of targets was achieved by 200 µL methanol/water (9:1) containing 150 mM sodium hexane sulfonate at pH 4.5. The method validation covered linearity, recovery, precision of intraday and interday, limits of detection, limits of quantitation, and repeatability. This established method was rapid, simple, environmentally friendly, and highly sensitive.     

Determine a Space-Dependent Source Term in a Time Fractional Diffusion-Wave Equation

This paper is devoted to identify a space-dependent source term in a multi-dimensional time fractional diffusion-wave equation from a part of noisy boundary data. Based on the series expression of solution for the direct problem, we improve the regularity of the weak solution for the direct problem under strong conditions. And we obtain the uniqueness of inverse space-dependent source term problem by the Titchmarsh convolution theorem and the Duhamel principle. Further, we use a non-stationary iterative Tikhonov regularization method combined with a finite dimensional approximation to find a stable source term. Numerical examples are provided to show the effectiveness of the proposed method.

     

New heterogeneous catalytic systems based on highly porous ceramic materials modified with immobilized d-metal cage complexes for H2 production from CH4

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Synthesis,crystal structure,DNA/bovine serum albumin binding and antitumor activity of two transition metal complexes with 4‐acylpyrazolone derivative

Two new complexes, namely [Cu₆L₆] ( 1 ) and [Zn(HL)₂] ( 2 ) (H₂L = N‐(1‐phenyl‐3‐methyl‐4‐propenylidene‐5‐pyrazolone)‐2‐furancarboxylic acid hydrazide), have been synthesized and characterized. Single crystal X‐ray analysis indicates that complex 1 has a hexanuclear structure and complex 2 exhibits a mononuclear structure. The DNA/bovine serum albumin (BSA) binding properties of complexes 1 and 2 were investigated by absorption spectroscopy and fluorescence quenching. Both complexes could effectively intercalate to DNA with calculated quenching constants of 2.6 × 10⁵ and 1.25 × 10⁵ M^?1, respectively. The quenching mechanism of the intrinsic fluorescence of BSA by the complexes was found to be a static one. The cytotoxicities of 1 and 2 were investigated in two human tumor cell lines, human esophageal cancer cells (Eca‐109) and cervical cancer cells (HeLa). Complex 1 exhibits higher antitumor activity than 2 . Furthermore, 1 can inhibit HeLa cells by inducing apoptosis and G0/G1 phase cell cycle arrest. All results demonstrate that 1 and 2 both have DNA/BSA binding capacity and antitumor activity.     

Hexanuclear 3d − 4f metal–organic cages assembled from a carboxylic acid‐functionalized tris‐triazamacrocycle for highly selective fluorescent sensing of picric acid

Two Ln^III ions are sandwiched by dinuclear Co^II building blocks derived from a tris‐triazamacrocyclic ligand bearing pendant carboxylic acid functionality, 1,3,5‐tris((4,7‐bis(2‐carboxyethyl)‐1,4,7‐triazacyclonon‐1‐yl)methyl)‐benzene (H₆L), giving rising to two nanoscale heterometallic metal–organic cages formulated as [Co₄Ln₂(LH_2.5)₂(H₂O)₄]·(ClO₄)₆·NO₃·nH₂O [Ln = Dy, n = 12 ( 1 ); Ln = Yb, n = 9 ( 2 )], whose internal cavity accommodates a guest NO₃^? anion. Their hexanuclear cage‐like architectures are maintained both in solution and solid states as confirmed by mass spectrum as well as X‐ray diffraction experiments. These two cages display ligand‐based fluorescence emissions and therefore both were chosen to be operated as fluorescent chemosensors for the detection of nitroaromatic compounds. Attractively, these metal–organic cages allow highly selective and sensitive detection of picric acid (PA) over other nitroaromatics in solution and suspension, and the fluorescence resonance energy transfer (FRET) between the cage probes and PA is mainly responsible for the remarkable detection efficiency.     

CS2 Reductive Coupling to Acetylenedithiolate by a Dinuclear Ytterbium(II) Complex

The activation of CS₂ is of interest in a broad range of fields and, more particularly, in the context of creating new C−C bonds. The reaction of the dinuclear ytterbium(II) complex [Yb₂L₄], 1 , [L=(OtBu)₃SiO⁻] with carbon disulfide led to the isolation of unprecedented reduction products. In particular, the crystallographic characterization of complex [Yb₂L₄(μ-C₂S₂)], 2 , provided the first example of an acetylenedithiolate ligand formed from metal reduction of CS₂. Computational studies indicated that this unprecedented reactivity can be ascribed to the unusual binding mode of CS₂²⁻ in the isolated “key intermediate” [Yb₂L₄(μ-CS₂)], 3 , which results from the dinuclear nature of 1 .     

The Linear Optical Unambiguous Discrimination of Hyperentangled Bell States Assisted by Time Bin

A linear optical unambiguous discrimination of hyperentangled Bell states is proposed for two‐photon systems entangled in both the polarization and momentum degrees of freedom (DOFs) assisted by time bin. This unambiguous discrimination scheme can completely identify 16 orthogonal hyperentangled Bell states using only linear optical elements, where the function of the auxiliary entangled Bell state is replaced by time bin. Moreover, the possibility of extending this scheme for distinguishing hyperentangled Bell states in n DOFs is discussed, and it shows that $2^{n+k+1}$ hyperentangled Bell states in n ( $n\ge 2$) DOFs can be distinguished with k ( $k<n$) auxiliary entangled states of additional DOFs by introducing a time delay, which decreases the auxiliary entanglement resource required for unambiguous discrimination of hyperentangled Bell state. Therefore, this scheme provides a new way for distinguishing hyperentangled states with current technology, which will extend the application of discrimination of hyperentangled states via linear optics to other quantum information protocols besides hyperdense coding schemes in the future.     

Hyphenone A,the first 3,3-diisoprenylated bicyclic polyprenylated acylphloroglucinols as Cav3.1 T-type calcium channel inhibitor from Hypericum henryi

Hyphenone A (1), a new type of bicyclic polyprenylated acylphloroglucinols (BPAPs) featured with an unprecedented 3,3-diisoprenylated 1,3,5-trione core, were characterized from the roots of Hypericum henryi together with two new congeners (hyphenones B–C, 2–3) and five known biosynthetic related PPAPs. Biogenetically, 1 should be derived from a novel 3,3,5,5-tetraisoprenylated MPAPs precursor. Their structures were elucidated by comprehensive spectroscopic data and X-ray diffraction. Moreover, 1–3 were identified as the first PPAPs type Ca_v3.1 T-type calcium channel (TTCC) inhibitors, with IC₅₀ values of 7.07, 6.19, and 5.47 μM, respectively.     

A Renal‐Clearable Duplex Optical Reporter for Real‐Time Imaging of Contrast‐Induced Acute Kidney Injury

Despite its high morbidity and mortality, contrast‐induced acute kidney injury (CIAKI) remains a diagnostic dilemma because it relies on in vitro detection of insensitive late‐stage blood and urinary biomarkers. We report the synthesis of an activatable duplex reporter (ADR) for real‐time in vivo imaging of CIAKI. ADR is equipped with chemiluminescence and near‐infrared fluorescence (NIRF) signaling channels that can be activated by oxidative stress (superoxide anion, O₂^.?) and lysosomal damage (N‐acetyl‐β‐d ‐glucosaminidase, NAG), respectively. By virtue of its high renal clearance efficiency (80 % injected doses after 24 h injection), ADR detects sequential upregulation of O₂^.? and NAG in the kidneys of living mice prior to a significant decrease in glomerular filtration rate (GFR) and tissue damage in the course of CIAKI. ADR outperforms the typical clinical assays and detects CIAKI at least 8 h (NIRF) and up to 16 h (chemiluminescence) earlier.     

Rhodium-catalyzed intramolecular hydroacylation of 1,2-disubstituted alkenes for the synthesis of 2-substituted indanones

The intramolecular hydroacylation of 1,2-disubstituted alkenes was considered to be a challenging task due to the side reactions resulted from the lack of additional substituent at 1-position and the low activity caused by the steric hindrance of substituent at 2-position, and an asymmetric version has not been considered possible due to problems associated with the racemization of the products. We have partially solved these problems. Catalyzed by an activated diphosphine-Rh complex and reacted in a selected dihalogenated solvent, the intramolecular hydroacylation of o-(2-arylvinyl)benzaldehydes provided the corresponding 2-aryl-1-indanones in high yields, and its asymmetric variant using o-(2-alkylvinyl)benzaldehydes afforded chiral 2-alkyl-1-indanones in high yields and with moderate enantioselectivities.