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With an ability to sustain optimal processing conditions in unsupervised settings, adaptive microfluidic systems would be less prone to artifacts and could eventually serve as reliable standardized biomedical tests at the point of care.Dopamine (DA) regulates several functions in the central nervous system and its depletion is responsible for psychological disorders like Parkinson's disease. Several analytical approaches have been presented for DA detection in pathological diagnosis. SERS spectroscopy is a highly promising technique for the sensitive detection of DA. However, an improvement in its detection in aqueous solution is highly desirable for reliable quantification in biological fluids. In this work, we explored a label-free SERS approach for DA detection, employing two conventional methods to synthesize Ag colloids reduction via citrates (c-AgNPs) and reduction via hydroxylamine (h-AgNPs), and SERS measurements were performed with a laser at 488 nm wavelength. this website Under these conditions, DA was identified through reproducible SERS spectra in the c-AgNP medium; however, the SERS spectra of DA in h-AgNP solution showed a completely different SERS profile. SERS band analysis revealed that DA in h-AgNPs was oxidized and converted into polydopamine (PDA), which was triggered after exposure to laser radiation. DA oxidation and PDA formation were followed over time through the SERS band profile at pH 7, 9 and 12. We found that in situ PDA formation started after 50 min of laser irradiation of DA at pH 7, while DA was quickly oxidized at pH 9 and 12. Here, we present a detailed SERS band analysis of PDA, which sheds light on the molecular steps in the pathway formation of the PDA structure. Spectroscopic analysis and characterization revealed that a long laser exposure time led to the formation of stable PDA complexes with AgNPs, which allowed us to propose a novel approach for synthesis of AgNP-PDA composites. In conclusion, to detect DA through a label-free SERS approach, c-AgNPs must be employed, while stable AgNP-PDA materials can be achieved with h-AgNPs and 488 nm laser excitation.The potential use of a statistical approach for the investigation of complex dissolved organic matter (DOM) sources in surface water within a recycled water system monitored by excitation-emission matrix (EEM) fluorescence spectroscopy is shown. The work in this manuscript utilize information extracted from EEM spectroscopy to characterize DOM in collected surface water samples along with a wastewater treatment plant to drinking water treatment plant, discussing that humic-like and protein-like DOM sources predominate in the investigated water samples. Five different fluorescent components were resolved, describing several different types of DOM with different excitation and emission spectra that were distinct among the watershed sampling sites and indicating the influences of anthropogenic impacts. In addition, these novel fluorescence parameters have potential to improve resolution to direct more targeted water quality monitoring approaches.A fundamental understanding of cyclodextrin-closo-dodecaborate inclusion complexes is of great interest in supramolecular chemistry. Herein, we report a systematic investigation on the electronic structures and intramolecular interactions of perhalogenated closo-dodecaborate dianions B12X122- (X = F, Cl, Br and I) binding to α-, β-, and γ-cyclodextrins (CDs) in the gas phase using combined negative ion photoelectron spectroscopy (NIPES) and density functional theory (DFT) calculations. The vertical detachment energy (VDE) of each complex and electronic stabilization of each dianion due to the CD binding (ΔVDE, relative to the corresponding isolated B12X122-) are determined from the experiments along α-, β- and γ-CD in the form of VDE (ΔVDE) 4.00 (2.10), 4.33 (2.43), and 4.30 (2.40) eV in X = F; 4.09 (1.14), 4.64 (1.69), and 4.69 (1.74) eV in X = Cl; 4.11 (0.91), 4.58 (1.38), and 4.70 (1.50) eV in X = Br; and 3.54 (0.74), 3.88 (1.08), and 4.05 (1.25) eV in X = I, respectively. All complexes have significantly hment from CDs. Energy decomposition analyses reveal that the electrostatic interaction plays a dominating role in contributing to the host-guest interactions for the X = F series partially due to the formation of a O/C-HX-B hydrogen bonding network, and the dispersion forces gradually become important with the increase of halogen size.Polyoxovanadates (POVs), as one of the most prominent members of polyoxometalates (POMs), have been subject to extensive studies by virtue of their aesthetically intriguing structures and potential applications in catalysis, magnetism, and optics, among others. In recent years, organo-functionalized POVs have received considerable attention due to the combination of the advantages of POVs with the importance of organic species. In this review, the key developments of polyoxovanadates and, particularly, the achievements that are related to polyoxovanadates modified with organic ligands and transition metal-organic ligand are summarized. Herein, we systematically introduce the structural features of organo-functionalized POVs and their main applications involved in the magnetism and catalysis aspects. Finally, the current challenges and future prospects in the design, synthesis, and property investigation of polyoxovanadates are also discussed.The adoption of a supramolecular approach in catalysis promises to address a number of unmet challenges, ranging from activity (unlocking of novel reaction pathways) to selectivity (alteration of the innate selectivity of a reaction, e.g. selective functionalization of C-H bonds) and regulation (switch ON/OFF, sequential catalysis, etc.). Supramolecular tools such as reversible association and recognition, pre-organization of reactants and stabilization of transition states upon binding offer a unique chance to achieve the above goals disclosing new horizons whose potential is being increasingly recognized and used, sometimes reaching the degree of ripeness for practical use. This review summarizes the main developments that have opened such new frontiers, with the aim of providing a guide to researchers approaching the field. We focus on artificial supramolecular catalysts of defined stoichiometry which, under homogeneous conditions, unlock outcomes that are highly difficult if not impossible to attain otherwise, namely unnatural reactivity or selectivity and catalysis regulation. The different strategies recently explored in supramolecular catalysis are concisely presented, and, for each one, a single or very few examples is/are described (mainly last 10 years, with only milestone older works discussed). The subject is divided into four sections in light of the key design principle (i) nanoconfinement of reactants, (ii) recognition-driven catalysis, (iii) catalysis regulation by molecular machines and (iv) processive catalysis.Complexes [Ru(η6-pcym)(bpydca)Cl]PF6 (Rudca) and [Ir(η5-Cp*)(bpydca)Cl]PF6 (Irdca) were developed as model compounds for the investigation of multi-targeted ester-functionalized half-sandwich ruthenium(ii) and iridium(iii) complexes; pcym = 1-methyl-4-(propan-2-yl)benzene (p-cymene), bpydca = 2,2'-bipyridine-4,4'-diyldimethanediyl bis(dichloroacetate), Cp* = pentamethylcyclopentadienyl. Aiming to understand the in-solution behaviour of these first-in-class complexes containing the pyruvate dehydrogenase kinase inhibitor dichloroacetate (dca) as the terminal bioactive substituent, several experiments were performed under aqueous conditions for Rudca and Irdca, as well as for compounds [Ru(η6-pcym)(bpyOH)Cl]PF6 (RuOH) and [Ir(η5-Cp*)(bpyOH)Cl]PF6 (IrOH), and acetyl analogues [Ru(η6-pcym)(bpyac)Cl]PF6 (Ruac) and [Ir(η5-Cp*)(bpyac)Cl]PF6 (Irac) bearing a different (biologically inactive) terminal substituent; bpyOH = 2,2'-bipyridine-4,4'-diyldimethanol, bpyac = 2,2'-bipyridine-4,4'-diyldimethanediyl diacetate. The experiments were also conducted in the presence of porcine liver esterase (PLE). All the six complexes were characterized by relevant techniques (e.g., NMR and mass spectrometry), including a single-crystal X-ray analysis of complexes Rudca, Ruac, RuOH and IrOH. Although designed as model compounds, Rudca, Irdca, RuOH and IrOH were also screened for their antiproliferative activity in four human cancer cell lines (HCT116 colon carcinoma, MDA-MB-231 and MCF-7 breast adenocarcinomas, DU145 prostate carcinoma), where the tested complexes did not show any effect (IC50 > 100 μM).A TsOH-catalyzed allenylation of pyrazolones with propargylic alcohols has been developed. The established reaction system is well tolerated by a wide scope of pyrazolones and propargylic alcohols. The process has the salient features of operational simplicity, facile scale-up and high yield. In particular, the integration of the pharmaceutical-related pyrazolone skeleton and the allenyl group into a single molecule not only enriches the structural diversity of the pyrazolone scaffold, but potentially also contributes to a broader spectrum of biological activity. Furthermore, it is easy to synthesize 3aa in gram-scale with the yield and efficiency basically maintained, making the practical application of this process more prominent.Correction for 'Mechanochemical tools for polymer materials' by Yinjun Chen et al., Chem. Soc. Rev., 2021, 50, 4100-4140, DOI 10.1039/D0CS00940G.A greener analytical technique for quantifying compounds in dense suspensions is needed for wastewater and environmental analysis, chemical or bio-conversion process monitoring, biomedical diagnostics, and food quality control, among others. In this work, we introduce a green, fast, one-step method called nanoextraction for extraction and detection of target analytes from sub-milliliter dense suspensions using surface nanodroplets without toxic solvents and pre-removal of the solid contents. With nanoextraction, we achieve a limit of detection (LOD) of 10-9 M for a fluorescent model analyte obtained from a particle suspension sample. The LOD is lower than that in water without particles (10-8 M), potentially due to the interaction of particles and the analyte. The high particle concentration in the suspension sample, thus, does not reduce the extraction efficiency, although the extraction process was slowed down up to 5 min. As a proof of principle, we demonstrate the nanoextraction for the quantification of model compounds in wastewater slurry containing 30 wt% solids and oily components (i.e. heavy oils). The nanoextraction and detection technology developed in this work may be used in fast analytical technologies for complex slurry samples in the environment, industrial waste, or in biomedical diagnostics.Intra-chain looping in complex environments is significant in advancing our understanding of biological processes in life. We adopt Langevin dynamics simulations to perform a comparative study of polymer looping kinetics in passive and active environments. From the analysis of looping quantities, including looping-unlooping times and looping probabilities, we unraveled the intriguing effects of active crowder size, activity and crowding. Firstly, we figured out the phase diagram involving a novel facilitation-inhibition transition in the parameter space of active crowder size and active force, and the two-fold roles of activity are clarified. In particular, we find that active particles of a size comparable to the polymer monomer are most favorable for facilitated looping, while those with a similar size to the polymer gyration radius impede the looping most seriously. Secondly, the underlying looping mechanisms in different active crowder size regimes are rationalized by the interplay among diffusion, polymer conformational change and the free-energy barrier.