Relationship between structural properties and biological activity of (-)-menthol and some menthyl esters.

Menthol is a naturally occurring cyclic terpene alcohol and is the major component of peppermint and corn mint essential oils extracted from Mentha piperita L. and Mentha arvensis L..

New cinnamic acid sugar esters as potential UVB filters: Synthesis, cytotoxicity, and physicochemical properties.

Cinnamic Acid Sugar Ester Derivatives (CASEDs) are a class of natural compounds that exhibit several interesting biological activities. However, to date, no examples of their use in sunscreen formulations have been reported. Here, we describe the synthesis of a series of novel cinnamic acid esters of glucose (4a-g), ribose (4h) and lactose (4i) starting from the respective acetals 3.

Bioconjugation of Synthetic Peptides onto Universal Chimeric Antigen Receptor T Cells for Targeted Cancer Immunotherapies.

The recent development of modular universal chimeric antigen receptor (CAR) T-cell platforms that use bifunctional adaptor intermediates to redirect engineered T-cell effector function has greatly expanded the capabilities of adoptive T-cell therapy, enabling safer and more comprehensive cancer treatment. However, universal CAR receptor systems rely on unstable transient recognition of tag-coupled intermediates for T-cell activation, and the array of targeting intermediates has been limited to antibodies and small molecules. Addressing these shortcomings, we engineered universal CAR T-cell receptors that can be covalently modified with synthetic biomaterials by accelerated SpyCatcher003-SpyTag003 chemistry for cancer-cell targeting.

Controlling spiral wave dynamics of the BZ system in a modified Oregonator model: From suppression to turbulence.

Spirals are a special class of excitable waves that have its significance in the understanding of cardiac arrests and neuronal transduction. In a theoretical model of the chemical Belousov-Zhabotinsky reaction system, we explore the dynamics of the spatiotemporal patterns that emerge out of competing reaction and diffusion phenomena. By modifying the existing mathematical models of the reaction kinetics, we have been able to explore the explicit effect of hydrogen ion concentration in the system, so as to achieve various regimes of wave activity, from stable spirals to oscillation death.

Polylactic Acid Micro/Nanoplastic Exposure Induces Male Reproductive Toxicity by Disrupting Spermatogenesis and Mitochondrial Dysfunction in Mice.

Although considered an "eco-friendly" biodegradable plastic, polylactic acid (PLA) microplastic (PLA-MP) poses a growing concern for human health, yet its effects on male reproductive function remain underexplored. This study investigated the reproductive toxicity of PLA in male mice and its potential mechanisms. To this end, our in vivo and in vitro experiments demonstrated that after degradation in the digestive system, a significant number of PLA-MP-derived nanoparticles could penetrate the blood-testis barrier (BTB) and localize within the spermatogenic microenvironment.

Understanding the Topology Freezing Temperature of Vitrimer-Like Materials through Complementary Structural and Rheological Analyses for Phase-Separated Network.

Vitrimers are sustainable cross-linked polymers characterized by an associative bond exchange mechanism within their network. A well-known feature of vitrimers is the Arrhenius dependence of the viscosity or relaxation time. Another important aspect is the existence of a topology-freezing temperature (), which represents a transition between the viscoelastic solid state and the malleable viscoelastic liquid state.

Clinicopathological and immunohistochemical analysis of the risk factors of recurrence of atypical lipomatous tumor/well-differentiated liposarcoma of the extremities.

Atypical lipomatous tumors/well-differentiated liposarcomas (ALT/WDLPS) are low-grade, slow-growing, and locally aggressive tumors. We investigated clinical outcomes and recurrence factors for ALT/WDLPS of the extremities. This is retrospective study across three institutions which included patients who underwent surgery for ALT/WDLPS from 2001 to 2019.

Synthesis and Characterization of Homo- and Heteroleptic Neptunium(IV) Heteroarylalkenolate Complexes.

Heteroleptic An (An = U, Np) chlorido-ketoenaminate complexes of the type [AnCl(TFB-BuA)(THF)] ( type: , ; TFB-BuA = 4-(-butylamino)-1,1,1-trifluorobut-3-en-2-one) and the homoleptic Np heteroarylalkenolate complexes [Np(PyTFP)] (, PyTFP = 1-(pyridin-2-yl)-3,3,3-trifluoroprop-1-en-2-ol) and [Np(DMOTFP)] (, DMOTFP = 1-(4,5-dimethyloxazol-2-yl)-3,3,3-trifluoroprop-1-en-2-ol) were synthesized and characterized (SC-XRD, NMR, Vis-NIR, MS). While their solid-state structures compare well to those of their uranium analogues, the behavior in solution showed significant differences. The binding motif of the DMOTFP ligand in complex can change to form two different complex isomers, as seen by paramagnetic chemical shifts in NMR experiments.

Nanoization of Technical Pesticides: Facile and Smart Pesticide Nanocapsules Directly Encapsulated through "On Site" Metal-Polyphenol Coordination Assembly for Improved Efficacy and Biosafety.

Facile pesticide nanocapsules were successfully prepared by directly encapsulating the antisolvent precipitation of pesticides through instantaneous "on site" coordination assembly of tannic acid and Fe, avoiding tedious preparation, time consumption, and large amounts of organic solvents. The pesticide nanocapsules showed excellent resistance to ultraviolet photolysis and rainwater washing owing to the nanocapsule walls. The smart pesticide nanocapsules exhibited the controlled release of pesticides under multidimensional stimuli, such as acidic/alkaline pH, glutathione, HO, phytic acid, laccase, tannase, and sunlight, which were related to the physiological and natural environments of crops, pests, and pathogens.

Relativistic CASPT2/RASPT2 Program along with DIRAC Software.

Exploring electronic states in actinide compounds is a critical aspect of nuclear science. However, considering relativistic effects and electron correlation in theoretical calculations poses a complex challenge. To tackle this, we developed the CASPT2/RASPT2 program along with the DIRAC program, enabling calculations of electron correlation methods using multiconfigurational perturbation theory with various relativistic Hamiltonians.

Gold(I)-Catalyzed 2-Deoxy-β-glycosylation via 1,2-Alkyl/Arylthio Migration: Synthesis of Velutinoside A Pentasaccharide.

2-Deoxy-β-glycosides are essential components of natural products and pharmaceuticals; however, the corresponding 2-deoxy-β-glycosidic bonds are challenging to chemically construct. Herein, we describe an efficient catalytic protocol for synthesizing 2-deoxy-β-glycosides via either IPrAuNTf-catalyzed activation of a unique 1,2--positioned C2--propargyl xanthate (OSPX) leaving group or (PhO)PAuNTf-catalyzed activation of a 1,2--C2--alkynylbenzoate (OABz) substituent of the corresponding thioglycosides. These activation processes trigger 1,2-alkyl/arylthio-migration glycosylation, enabling the synthesis of structurally diverse 2-deoxy-β-glycosides under mild reaction conditions.

Clinical Activity of Mitogen-Activated Protein Kinase Inhibitors in Patients With MAP2K1 (MEK1)-Mutated Metastatic Cancers.

Purpose: MAP2K1/MEK1 mutations are potentially actionable drivers in cancer. MAP2K1 mutations have been functionally classified into three groups according to their dependency on upstream RAS/RAF signaling. However, the clinical efficacy of mitogen-activated protein kinase (MAPK) pathway inhibitors (MAPKi) for MAP2K1-mutant tumors is not well defined.

Surface-Sensitive Waveguide Imaging for In Situ Analysis of Membrane Protein Binding Kinetics.

Ligand binding to membrane proteins initiates numerous therapeutic processes. Surface plasmon resonance (SPR), a popular method for analyzing molecular interactions, has emerged as a promising tool for in situ determination of membrane protein binding kinetics owing to its label-free detection, high surface sensitivity, and resistance to intracellular interference. However, the excitation of SPR relies on noble metal films, typically gold, which are biologically incompatible and can cause fluorescence quenching.

Understanding the Dual Role of Macrophages in Tumor Growth and Therapy: A Mechanistic Review.

Macrophages are heterogeneous cells that are the mediators of tissue homeostasis. These immune cells originated from monocytes and are classified into two basic categories, M1 and M2 macrophages. M1 macrophages exhibit anti-tumorous inflammatory reactions due to the behavior of phagocytosis.

Where Does the Proton Go? Structure and Dynamics of Hydrogen-Bond Switching in Aminophosphine Chalcogenides.

Aminophosphates are the focus of research on prebiotic phosphorylation chemistry. Their bifunctional nature also makes them a powerful class of organocatalysts. However, the structural chemistry and dynamics of proton-binding in phosphorylation and organocatalytic mechanisms are still not fully understood.

Synergistic Cancer Photoimmunotherapy by Harnessing Near-Infrared-Activated Nanoparticles Containing Charge Transfer Complexes.

Phototherapy - which includes photothermal therapy (PTT) and photodynamic therapy (PDT) - has evoked interest as a promising cancer treatment modality on account of its noninvasiveness, spatiotemporal precision, and minimal side effects. C. Wang et al.

Force-Trainable Liquid Crystal Elastomer Enabled by Mechanophore-Induced Radical Polymerization.

In nature, organisms adapt to environmental changes through training to learn new abilities, offering valuable insights for developing intelligent materials. However, replicating this adaptive learning in synthetic materials presents a significant challenge. This study introduces a feasible approach to train liquid crystal elastomers (LCEs) by integrating a mechanophore tetraarylsuccinonitrile (TASN) into their main chain, addressing the challenge of enabling synthetic materials to exchange substances with their environment.

New Layered Boride NiPtB ( = 0.5) with a Ternary Derivative Structure of MoB.

A novel ternary boride, NiPtB ( = 0.5), was obtained by argon-arc melting of the elements followed by annealing at 750 °C. It exhibits a new structure type with the space group ( = 2.

Rational Design of Nanozymes for Engineered Cascade Catalytic Cancer Therapy.

Nanozymes have shown significant potential in cancer catalytic therapy by strategically catalyzing tumor-associated substances and metabolites into toxic reactive oxygen species (ROS) , thereby inducing oxidative stress and promoting cancer cell death. However, within the complex tumor microenvironment (TME), the rational design of nanozymes and factors like activity, reaction substrates, and the TME itself significantly influence the efficiency of ROS generation. To address these limitations, recent research has focused on exploring the factors that affect activity and developing nanozyme-based cascade catalytic systems, which can trigger two or more cascade catalytic processes within tumors, thereby producing more therapeutic substances and achieving efficient and stable cancer therapy with minimal side effects.

Functionalized Terthiophene as an Ambipolar Redox System: Structure, Spectroscopy, and Switchable Proton-Coupled Electron Transfer.

Organic redox systems that can undergo oxidative and reductive (ambipolar) electron transfer are elusive yet attractive for applications across synthetic chemistry and energy science. Specifically, the use of ambipolar redox systems in proton-coupled electron transfer (PCET) reactions is largely unexplored but could enable "switchable" reactivity wherein the uptake and release of hydrogen atoms are controlled using a redox stimulus. Here, we describe the synthesis and characterization of an ambipolar functionalized terthiophene (TTH) bearing methyl thioether and phosphine oxide groups that exhibits switchable PCET reactivity.

Probing Impact of Support Pore Diameter on Three-phase Interfaces of Pt/C Catalysts by Molecular Dynamic Simulation.

Investigating how the size of carbon support pores influences the three-phase interface of platinum (Pt) particles in fuel cells is essential for enhancing catalyst utilization. This study employed molecular dynamics simulations and density functional theory calculation to examine the effects of mesoporous carbon support size, specifically its pore diameter, on Nafion ionomer distribution, as well as on proton and gas/liquid transport channels, and the utilization of Pt active sites. The findings show that when Pt particles are located within the pores of carbon support (Pt/PC), there is a significant enhancement in the spatial distribution of Nafion ionomer, along with a reduction in encapsulation around the Pt particles, compared to when Pt particles are positioned on the surface or in excessively large pores of the carbon support.

A Fast-Pass, Desorption Electrospray Ionization Mass Spectrometry Strategy for Untargeted Metabolic Phenotyping.

Desorption electrospray ionization mass spectrometry imaging (DESI-MSI) provides direct analytical readouts of small molecules that can be used to characterize the metabolic phenotypes of genetically engineered bacteria. In an effort to accelerate the time frame associated with the screening of mutant libraries, we have developed a high-throughput DESI-MSI analytical workflow implementing a single raster line-scan strategy that facilitates the collection of location-resolved molecular information from engineered strains on a subminute time scale. Evaluation of this "Fast-Pass" DESI-MSI phenotyping workflow on analytical standards demonstrated the capability of acquiring full metabolic profiling information with a throughput of ∼40 s per sample.

Circular Polymer Designed by Regulating Entropy: Spiro-Valerolactone-Based Polyesters with High Gas Barriers and Adhesion Strength.

Enthalpy is often the focal point when designing monomers for polymer circularity, but much less is explored on how entropy can be exploited to create polymers with synergistic circularity and properties. Here, we design a series of spiro-lactones (SLs) with closed-chain cycloalk(en)yl substituents at the α,α-position of δ-valerolactone (δVL), which, when combined with the parent δVL and -α,α-dialkyl-substituted δVL with open-chain alkyl groups, provide a desired platform for exploring the circular polymer design by focusing on the entropy change of polymerization. These SLs exhibit finely balanced (de)polymerizability that is regulated chiefly by entropy differentiation, allowing both the facile synthesis of polyester PSLs ( up to 1000 kg mol) in a living fashion and selective depolymerization of the PSLs to completely recover monomers under mild conditions (using a recyclable catalyst at 100 °C).

Nickel-Catalyzed Electroreductive Sulfuration of Alkyl Alcohols with Pyridyl Thioesters.

We demonstrate here an efficient and facile Ni-catalyzed electrochemical cross-electrophile thiolation approach for readily available alkyl alcohols with pyridyl thioesters. This C(sp)-S bond-forming modular strategy displays extensive substrate adaptability and good functional group tolerance, which allows the production of a range of alkyl sulfides with specific chemoselectivity. Furthermore, the potential applications of this methodology are illustrated by last-stage modification of bioactive molecules and sulfinylative cross-couplings.

Accumulation of Water-Soluble Polysaccharides during Lychee Pulp Fermentation with Involves Endoglucanase Expression.

In the current work, lychee pulp was subjected to ATCC 14917 fermentation, leading to a substantial increase (2.32-2.67-fold) in water-soluble polysaccharides (WSP).