Two-Dimensional Nanoarchitectonics of End-on Oligomers with Versatile Structures and Tunable Negative Differential Resistance.

Maximizing the molecular information density requires simultaneously functionalizing distinct monomers and their coupling connections. However, current synthesis generally focuses on distinct monomers rather than coupling reactions because the multistep reactions significantly escalate the synthetic complexity in an exponential increase. Here, we report the two-dimensional nanoarchitectures (2DNs) of end-on oligomers, with versatile molecular structures and negative differential resistance (NDR), synthesized by programmed and surface-initiated step electrosynthesis based on the simultaneous utilization of six reactions including cross- and homocouplings.

Correction: Polydopamine-capped AgNPs as a novel matrix overcoming the ion suppression of phosphatidylcholine for MALDI MS comprehensive imaging of glycerophospholipids and sphingolipids in impact-induced injured brain.

Correction for 'Polydopamine-capped AgNPs as a novel matrix overcoming the ion suppression of phosphatidylcholine for MALDI MS comprehensive imaging of glycerophospholipids and sphingolipids in impact-induced injured brain' by Chao Han , , 2019, , 6304-6312, https://doi.org/10.1039/C9AN01361J.

Single-Molecule Exchange inside a Nanocage Provides Insights into the Origin of π-π Interactions.

The attractive interactions between aromatic rings, also known as π-π interactions, have been widely used for decades. However, the origin of π-π interactions remains controversial due to the difficulties in experimentally measuring the weak interactions between π-systems. Here, we construct an elaborate system to accurately compare the strength of the π-π interactions between phenylalanine derivatives via molecular exchange processes inside a protein nanopore.

Ultra-High-Performance Liquid Chromatography-Electrospray Ionization-High-Resolution Mass Spectrometry for Distinguishing the Origin of Ellagic Acid Extracts: Pomegranate Peels or Gallnuts.

Ellagic acid, known for its various biological activities, is widely used. Ellagic acid from pomegranate peels is safe for consumption, while that from gallnuts is only suitable for external use. However, there is currently no effective method to confirm the source of ellagic acid.

Nanoarchitectonics on Electrosynthesis and Assembly of Conjugated Metallopolymers.

In contrast to edge-on and face-on orientations, end-on uniaxial conjugated polymers have the theoretical possibility of providing a macroscopic crystalline film. However, their fabrication is insurmountable due to sluggishly thermodynamic equilibrium states. Herein, we report the programmatic pathway to fabricate nanoarchitectonics on end-on uniaxial conjugated metallopolymers by surface-initiated simultaneous electrosynthesis and assembly.

Rapid, Selective Extraction of Silver from Complex Water Matrices with a Metal-Organic Framework/Oligomer Composite Constructed via Supercritical CO.

Every year vast quantities of silver are lost in various waste streams; this, combined with its limited, diminishing supply and rising demand, makes silver recovery of increasing importance. Thus, herein, we report a controllable, green process to produce a host of highly porous metal-organic framework (MOF)/oligomer composites using supercritical carbon dioxide (ScCO ) as a medium. One resulting composite, referred to as MIL-127/Poly-o-phenylenediamine (PoPD), has an excellent Ag adsorption capacity, removal efficiency (>99 %) and provides rapid Ag extraction in as little as 5 min from complex liquid matrices.

Composition and sequence-controlled conductance of crystalline unimolecular monolayers.

Understanding how the charge travels through sequence-controlled molecules has been a formidable challenge because of simultaneous requirements in well-controlled synthesis and well-manipulated orientation. Here, we report electrically driven simultaneous synthesis and crystallization as a general strategy to study the conductance of composition and sequence-controlled unioligomer and unipolymer monolayers. The structural disorder of molecules and conductance variations on random positions can be extremely minimized, by uniform synthesis of monolayers unidirectionally sandwiched between electrodes, as an important prerequisite for the reproducible measurement on the micrometer scale.

A hydrophobic Cu/CuO sheet catalyst for selective electroreduction of CO to ethanol.

Electrocatalytic reduction of carbon monoxide into fuels or chemicals with two or more carbons is very attractive due to their high energy density and economic value. Herein we demonstrate the synthesis of a hydrophobic Cu/CuO sheet catalyst with hydrophobic n-butylamine layer and its application in CO electroreduction. The CO reduction on this catalyst produces two or more carbon products with a Faradaic efficiency of 93.

Liposomes embedded with PEGylated iron oxide nanoparticles enable ferroptosis and combination therapy in cancer.

Ferroptosis, an iron-dependent regulated cell death process driven by excessive lipid peroxides, can enhance cancer vulnerability to chemotherapy, targeted therapy and immunotherapy. As an essential upstream process for ferroptosis activation, lipid peroxidation of biological membranes is expected to be primarily induced by intrabilayer reactive oxygen species (ROS), indicating a promising strategy to initiate peroxidation by improving the local content of diffusion-limited ROS in the lipid bilayer. Herein, liposomes embedded with PEG-coated 3 nm γ-FeO nanoparticles in the bilayer (abbreviated as Lp-IO) were constructed to promote the intrabilayer generation of hydroxyl radicals (•OH) from hydrogen peroxide (HO), and the integration of amphiphilic PEG moieties with liposomal bilayer improved lipid membrane permeability to HO and •OH, resulting in efficient initiation of lipid peroxidation and thus ferroptosis in cancer cells.

Triazine-Porphyrin-Based Hyperconjugated Covalent Organic Framework for High-Performance Photocatalysis.

Covalent organic frameworks (COFs) with porphyrins as structural units are a new kind of porous organic polymers, which have a regular and ordered structure, abundant porosity, and good stability. In the past, the construction of porphyrin COFs was generally synthesized by routes such as a Schiff base reaction. Here, we report a new COF structure by linking the porphyrin with the triazine ring.

Crystalline Unipolymer Monolayer with High Modulus and Conductivity.

The synthesis of crystalline polymer with a well-defined orientated state and a two-dimensional crystalline size beyond a micrometer will be essential to achieve the highest physical feature of polymer material but remain challenging. Herein, we show the synthesis of the crystalline unipolymer monolayer with an unusual ultrahigh modulus that is higher than the ITO substrate and high conductance by simultaneous electrosynthesis and manipulation. We find that the polymer monolayer has fully extended in the vertical and unidirectional orientation, which is proposed to approach their theoretically highest density, modulus, and conductivity among all aggregation formations of the current polymer.

Astragaloside IV promotes pharmacological effect of seeds on isoproterenol-induced cardiomyopathy in rats by synergistically modulating the myosin motor.

seeds (DS), (AM), and their formulas are widely used to treat heart failure caused by various cardiac diseases in traditional Chinese medicine practice. However, the molecular mechanism of action of DS and AM has not been completely understood. Herein, we first used mass spectrometry coupled to UPLC to characterize the chemical components of DS and AM decoctions, then applied MS-based quantitative proteomic analysis to profile protein expression in the heart of rats with isoproterenol-induced cardiomyopathy (ISO-iCM) before and after treated with DS alone or combined with AM, astragaloside IV (AS4), calycosin-7-glucoside (C7G), and Astragalus polysaccharides (APS) from AM.

Amphiphilic Aminated Derivatives of [60]Fullerene as Potent Inhibitors of Tumor Growth and Metastasis.

Malignant proliferation and metastasis are the hallmarks of cancer cells. Aminated [70]fullerene exhibits notable antineoplastic effects, promoting it a candidate for multi-targeted cancer drugs. It is an urgent need to reveal the structure-activity relationship for antineoplastic aminated fullerenes.

Abplatin inhibited tumor growth on a patient derived cancer model of hepatocellular carcinoma and its comparative multi-omics study with cisplatin.

Background: Cisplatin, the alkylating agent of platinum(II) (Pt(II)), is the most common antitumor drug in clinic; however, it has many side effects, therefore it is higly desired to develop low toxicity platinum(IV) (Pt(IV)) drugs. Multi-omics analysis, as a powerful tool, has been frequently employed for the mechanism study of a certain therapy at the molecular level, which might be helpful for elucidating the mechanism of platinum drugs and facilitating their clinical application.

Methods: Strating form cisplatin, a hydrophobic Pt(IV) prodrug (CisPt(IV)) with two hydrophobic aliphatic chains was synthesized, and further encapsulated with a drug carrier, human serum albumin (HSA), to form nanoparticles, namely AbPlatin.

Design and synthesis of a deep tissue penetrating near-infrared two-photon fluorescence probe for the specific detection of NQO1.

NAD(P)H:quinone oxidoreductase 1 (NQO1) is overexpressed in a broad range of human tumors but remains difficult to study. Herein, we report a novel two-photon fluorescent probe with NIR emission for NQO1 detection. The probe demonstrated superior analytical performance with a large Stokes shift and deep tissue penetration.

Real-time analysis of metabolites in vivo by online extraction electrospray ionization mass spectrometry coupled to microdialysis.

In vivo and real-time analysis could reflect a more real biological state, which was of great significance to the study of complex life processes. In this work, we constructed an online extraction electrospray ionization (OE-ESI) ion source as the interface of microdialysis and mass spectrometry, which realized real-time analysis of metabolites in vivo without sample pretreatment process. The ion source was consisted of three coaxial capillaries, and the parameters of the ion source were optimized.

G-quadruplex inducer/stabilizer pyridostatin targets SUB1 to promote cytotoxicity of a transplatinum complex.

Pyridostatin (PDS) is a well-known G-quadruplex (G4) inducer and stabilizer, yet its target genes have remained unclear. Herein, applying MS proteomics strategy, we revealed PDS significantly downregulated 22 proteins but upregulated 16 proteins in HeLa cancer cells, of which the genes both contain a number of G4 potential sequences, implying that PDS regulation on gene expression is far more complicated than inducing/stabilizing G4 structures. The PDS-downregulated proteins consequently upregulated 6 proteins to activate cyclin and cell cycle regulation, suggesting that PDS itself is not a potential anticancer agent, at least toward HeLa cancer cells.

Investigation of the sublimation mechanism of GeSe and GeS.

GeSe and GeS have emerged as promising light-harvesting materials for photovoltaics due to their attractive optoelectronic properties, non-toxic and earth-abundant constituents, and excellent stability. Here we unveil the diatomic molecule sublimation mechanism of GeSe and GeS that directly guides the optimization of GeSe and GeS solar-cell fabricated the close-space sublimation method.

Production of Piperidine and δ-Lactam Chemicals from Biomass-Derived Triacetic Acid Lactone.

Piperidine and δ-Lactam chemicals have wide application, which are currently produced from fossil resource in industry. Production of this kind of chemicals from lignocellulosic biomass is of great importance, but is challenging and the reported routes give low yield. Herein, we demonstrate the strategy to synthesize 2-methyl piperidine (MP) and 6-methylpiperidin-2-one (MPO) from biomass-derived triacetic acid lactone (TAL) that is produced microbially from glucose.

Protecting-Group-Free Iterative Exponential Growth Method for Synthesizing Sequence-Defined Polymers.

As a main synthetic strategy for monodisperse sequence-defined polymers, the known iterative exponential growth (IEG) methods were all developed on protecting-group chemistry, where the additional deprotection reactions increased their synthetic steps and decreased their atom economy. In this study, we developed a protecting-group-free IEG method for the formation of sequence-defined polymers by combining three orthogonal click reactions of copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC), sulfur-fluoride exchange reaction (SuFEx), and Ugi four-component reaction (Ugi-4CR). In this approach, oligomer synthesis began with three parallel CuAAC, SuFEx, and Ugi-4CR couplings among three monomers each with two orthogonal clickable end groups.

Cellular Uptake, Organelle Enrichment, and Antioxidation of Fullerene Derivatives, Mediated by Surface Charge.

Hydrophilic fullerene derivatives get notable performance in various biological applications, especially in cancer therapy and antioxidation. The biological behaviors of functional fullerenes are much dependent on their surface physicochemical properties. The excellent reactive oxygen species-scavenging capabilities of functional fullerenes promote their outstanding performances in inhibiting pathological symptoms associated with oxidative stress, including neurodegenerative diseases, cardiovascular diseases, acute and chronic kidney disease, and diabetes.

Aminated Fullerene Abrogates Cancer Cell Migration by Directly Targeting Myosin Heavy Chain 9.

Functional fullerene derivatives exhibit fantastic inhibitory capabilities against cancer survival and metastasis, but the absence of clarified biological molecular targets and ambiguous regulation mechanisms set barriers for their clinical transformation. Cancer metastasis is the primary cause of mortality and initiated with increased cell migration, making cell motility regulation a high-value therapeutic target in precision medicine. Herein, a critical molecular target of the aminated fullerene derivative (C-EDA), myosin heavy chain 9 (MYH9), was initially identified by a pull-down assay and MS screening.

Red Emissive Carbon Dots Prepared from Polymers as an Efficient Nanocarrier for Coptisine Delivery in vivo and in vitro.

Negatively charged fluorescent carbon dots (CDs, E =608 nm) were hydrothermally prepared from thiophene phenylpropionic acid polymers and then successfully loaded with the positively charged anticancer cargo coptisine, which suffers from poor bioavailability. The formed CD-coptisine complexes were thoroughly characterized by particle size, morphology, drug loading efficiency, drug release, cellular uptake and cellular toxicity in vitro and antitumor activities in vivo. In this nano-carrier system, red emissive CDs possess multiple advantages as follows: 1) high drug loading efficiency (>96 %); 2) sustained drug release; 3) enhanced drug efficacy towards cancer cells; 4) EPR effect; 5) drug release tracing with near-infrared imaging.

Co-Incorporated Mesoporous Carbon Material-Assisted Laser Desorption/Ionization Ion Source as an Online Interface of In Vivo Microdialysis Coupled with Mass Spectrometry.

The combination of microdialysis and mass spectrometry (MS) provides the potential for rapidly monitoring diverse metabolites in vivo. Unfortunately, the high concentration of salt in biological microdialysates hindered the sensitive and online detection of these small molecular compounds. In this study, we synthesized Co-incorporated mesoporous carbon material (Co-NC) and developed a Co-NC-assisted laser desorption/ionization (LDI) ion source as an online interface of in vivo microdialysis coupled with MS for the direct analysis of diverse metabolites in microdialysates.

Proteasome-Independent Protein Knockdown by Small-Molecule Inhibitor for the Undruggable Lung Adenocarcinoma.

Therapeutic target identification and corresponding drug development is a demanding task for the treatment of lung adenocarcinoma, especially the most malignant proximal-proliferative subtype without druggable protein kinase mutations. Using a cell-SELEX-generated aptamer, we discovered a new tumor driver protein, leucine-rich pentatricopeptide repeat-containing protein (LRPPRC), which is specifically overexpressed in the most lethal subtype of lung adenocarcinoma. Targeted LRPPRC protein knockdown is a promising therapeutic strategy for the undruggable LUAD (lung adenocarcinoma).