Glycol Moieties Research Articles

Highly efficient dip catalysts using bacterial cellulose impregnated with self-crosslinked glycol chitosan and silver nanoparticles for 4-nitrophenol reduction

The application of environmentally friendly and sustainable catalysts requires efficient and safe preparation methods using cheap and renewable materials. Although many metal nanoparticles (NPs) have low colloidal stability, they are still very effective as catalysts. Using a straightforward method, we developed a bacterial cellulose–glycol chitosan–silver (BC–GCS–Ag) nanocomposite, by introducing both AgNPs and self-crosslinked GCS within the BC network. Self-crosslinking of GCS occurred during the formation of AgNPs by employing the glycol moieties for reduction to produce aldehyde functionalities, thereby forming Schiff's base bonds within the GCS structure. Using GCS, well-defined AgNPs within the BC matrix. The formation of AgNPs and the self-crosslinking of GCS were characterized using UV–visible spectroscopy, Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The results showed that spherical AgNPs with a mean diameter of 10 nm exhibited a well-organized structure within the BC–GCS matrix. The BC–GCS–Ag nanocomposite was applied as dip catalyst for the reduction of 4-nitrophenol (4NP) to 4-aminophenol (4AP), chosen as a model reaction. The results showed that the catalytic reaction was completed within 4 min, with high reusability (10 times) and without loss of catalyst. The reaction followed pseudo-first-order kinetics with a high rate constant of 0.582 min−1. Therefore, the BC–GCS–Ag dip catalyst is an attractive alternative for environmentally friendly and sustainable catalysis, owing to its exceptional catalytic performance, high recyclability, and stability, as well as the minimal environmental footprint of the supporting materials.

Covalent Organic Frameworks Interfacial Modification of Ceramic Electrolytes for Enhanced Electrochemical Performance

AbstractThe interface instability between inorganic ceramic electrolytes and lithium metal anodes seriously affects the cycling behavior of high‐performance lithium‐metal batteries. Herein, an in situ interfacial modification strategy is proposed to build the precise hybrid organic/inorganic lithium‐ion conducting layer where the Li1.3Al0.3Ti1.7(PO4)3 (LATP) particle surface is anchored by ion‐conducting covalent organic frameworks (COF) with affluent poly(ethylene glycol) (PEG) moieties. This interlayer features ion transport regulation to avoid high interfacial resistance and enhances interfacial stability by building a functional COF‐based shield against electrons. These as‐prepared particles are employed to fabricate flexible quasi‐solid electrolyte membranes interconnected by polytetrafluoroethylene binder based on the dry process. The obtained membranes perform two‐fold increase in ion conductivity at 30 °C of 2.55 × 10−3 S cm−1 and the prolonged lithium deposition up to 1000 h compared to the pristine, which are attributed to synergistic effects in the inorganic/organic phase. Moreover, an integrated cathode/electrolytes design is proposed and exhibits excellent cycling performance with capacity retention of 98.8% after 200 cycles at 1 C. The corresponding pouch cells can light up LED after bending and recovery. This research provides new insights into the great potential of fabricating soft ceramic‐based membranes in a low‐cost and green way for highly‐stable lithium‐metal batteries.

Delivery of N-heterocyclic drugs, acids, phenols, and thiols via Tailor−made Self−immolative linkers

Heterocyclic drugs display diverse pharmacological activities and metabolic stability. However, their poor solubility and pharmacokinetic properties often compromise bioavailability and clinical outcomes. Nevertheless, the prodrug approach provides a viable strategy to overcome unwanted attributes of drug candidates. In this proof-of-concept study, we report the synthesis and biological evaluation of glycol methylene-bridged phosphate (GMBP) prodrugs developed for heterocyclic drug delivery. Through methylene bridging, the heterocyclic nitrogen was directly attached to the phosphate, whereas the glycol moiety enabled drug release via cyclization, as confirmed by 31P NMR spectroscopy. Additional prodrugs of carboxylic acids, phenols, and thiols confirmed the broad application scope of our GMPB approach. Heterocyclic GMBP prodrugs were stable in aqueous buffers and activated by phospholipase CAL-B in vitro. Select prodrugs, including zidovudine prodrug 33, were even more potent (3 nM on HIV-1) than the parent compound. These findings demonstrate that our GMBP approach is not only feasible but also highly versatile.

Modulating Surface Cation Concentration via Tuning the Molecular Structures of Ethylene Glycol-Functionalized PEDOT for Improved Alkaline Hydrogen Evolution Reaction.

The sluggish catalytic kinetics of nonprecious metal-based electrocatalysts often hinder them from achieving efficient hydrogen evolution reactions (HERs). Poly(3,4-ethylenedioxythiophene) (PEDOT) and its derivatives have been promising materials for various electrochemical applications. Nevertheless, previous studies have demonstrated that PEDOT coatings can be detrimental to HER performance. In this study, we investigated the alkaline HER efficiency of nickel foam coated with three types of ethylene glycol (EG)-functionalized EDOT. Specifically, EDOT derivatives bearing hydroxyl (-OH) and methoxy (-OCH3) end groups on the EG side chain and molecules containing two EDOT units are interconnected via EG moieties. EG groups are selected due to their strong interaction with alkali metal cations. Intriguingly, improved HER performance is observed on all electrodes coated with EG-functionalized EDOTs. Electrochemical impedance spectroscopy, electrochemical quartz crystal microbalance with dissipation, and XPS analysis are employed to explore the origin of enhanced HER efficiency. The results suggest the EG moieties can induce locally concentrated ions near the electrode surface and facilitate water dissociation through noncovalent interactions. The influence of EG chain length is systematically investigated by synthesizing molecules with di-EG, tetra-EG, and hexa-EG functionalities. This study highlights the importance of molecular design in modifying electrode surface properties to promote alkaline HER.

Late-Stage Desulfurization Enables Rapid and Efficient Solid-Phase Synthesis of Cathepsin-Cleavable Linkers for Antibody-Drug Conjugates.

The synthesis of linker-payloads is a critical step in developing antibody-drug conjugates (ADCs), a rapidly advancing therapeutic approach in oncology. The conventional method for synthesizing cathepsin B-labile dipeptide linkers, which are commonly used in ADC development, involves the solution-phase assembly of cathepsin B-sensitive dipeptides, followed by the installation of self-immolative para-aminobenzyl carbonate to facilitate the attachment of potent cytotoxic payloads. However, this approach is often low yield and laborious, especially when extending the peptide chain with components like glutamic acid to improve mouse serum stability or charged amino acids or poly(ethylene glycol) moieties to enhance linker hydrophilicity. Here, we introduce a novel approach utilizing late-stage desulfurization chemistry, enabling safe, facile, and cost-effective access to the cathepsin B-cleavable linker, Val-Ala-PABC-MMAE, on resin for the first time.

Amphiphilic Dendronized Copolymer-Encapsulated Au, Ag and Pd Nanoparticles for Catalysis in the 4-Nitrophenol Reduction and Suzuki-Miyaura Reactions.

The branched structures of dendronized polymers can provide good steric stabilization for metal nanoparticle catalysts. In this work, an amphiphilic dendronized copolymer containing hydrophilic branched triethylene glycol moieties and hydrophobic branched ferrocenyl moieties is designed and prepared by one-pot ring-opening metathesis polymerization, and is used as the stabilizer for metal (Au, Ag and Pd) nanoparticles. These metal nanoparticles (Au nanoparticles: 3.5 ± 3.0 nm; Ag nanoparticles: 7.2 ± 4.0 nm; Pd nanoparticles: 2.5 ± 1.0 nm) are found to be highly active in both the 4-nitrophenol reduction and Suzuki-Miyaura reactions. In the 4-nitrophenol reduction, Pd nanoparticles have the highest catalytic ability (TOF: 2060 h-1). In addition, Pd nanoparticles are also an efficient catalyst for Suzuki-Miyaura reactions (TOF: 1980 h-1) and possess good applicability for diverse substrates. The amphiphilic dendronized copolymer will open a new door for the development of efficient metal nanoparticle catalysts.

Novel magnetic bimetallic AuCu catalyst for reduction of nitroarenes and degradation of organic dyes.

Herein, core-shell magnetic nanoparticles are modified with imidazolium-tagged phosphine and propylene glycol moieties and used for the stabilization of bimetallic AuCu nanoparticles. The structure and morphology of the prepared material are identified with SEM, TEM, XRD, XPS, atomic absorption spectroscopy, Fourier translation infrared spectroscopy, and a vibrating sample magnetometer. This hydrophilic magnetic bimetallic catalyst is applied in the reduction of toxic nitroarenes and reductive degradation of hazardous organic dyes such as methyl orange (MO), methyl red (MR), and rhodamine B (RhB), as well as in the degradation of tetracycline (TC). This magnetic AuCu catalyst indicated superior activity in all three mentioned reactions in comparison with its single metal Au and Cu analogs. This catalyst is recycled for 17 consecutive runs in the reduction of 4-nitrophenol to 4-aminophenol without a significant decrease in catalytic activity and recycled catalyst is characterized.

Surface Modification of Montmorillonite Clay Towards the Fabrication of Nanocomposites for Engineering Applications

Montmorillonite (MMT) is a layered clay mineral composed of silica and alumina sheets with a layer thickness of about 1 nm qualifies it as a two-dimensional nanomaterial. MMT is found in natural clay ores in the Murunkan, Kirinda, and Okanda areas in Sri Lanka. Nanocomposites with enhanced physical and mechanical properties can be prepared by dispersing MMT in a polymer matrix. However, the hydrophilic nature of MMT hinders the incorporation of MMT into hydrophobic polymer matrices. Hence, a suitable surface modification is required to make MMT compatible with polymers. The present study was based on the preparation and analysis of organically modified calcium Montmorillonite (Ca-MMT)-polypropylene nanocomposites as a green technology initiative. Homo-ionic Ca-MMT was prepared by treating commercial MMT-K10 with a CaCl2 solution. The predominant exchangeable divalent cations present in MMT-K10 and Ca-MMT were determined using AAS. The cation exchange capacity of Ca-MMT was about two times greater than that of MMT-K10. Furthermore, XRD analysis showed a slight increase in d- spacing of Ca-MMT compared to MMT-K10. A novel ligand, triethylene glycol dodecyl methyl ether was synthesized by treating triethylene glycol monomethyl ether (TGME) with 50% w/w aqueous solution of sodium hydroxide followed by 1-bromododecane with the molar ratio of TGME:NaOH:1-bromododecane in 1:2:2. The crude product was purified by column chromatography and characterized by FTIR and GCMS analysis. Hydrophilic Ca-MMT was surface modified with the organic ligand presumably via the coordination of triethylene glycol moiety with Ca2+ cations at the outer edge of the MMT particles. The long aliphatic chains in the periphery of the modified MMT particle make it more organophilic. Modified Ca-MMT was characterized by XRD, TGA, and FTIR analysis. The XRD revealed a slight increase in the d-spacing related to the 001 plane of modified Ca-MMT compared to unmodified clay. The effect of modified Ca-MMT loadings (0.5%, 1%, and 1.5%) on the mechanical properties of the nanocomposite was studied. The results implied an enhancement of the mechanical properties in terms of impact resistance, hardness, and flexural properties in the nanocomposite compared to the virgin polymer. The fabricated nanocomposite is a promising engineering material that may have applications in automotive, construction, and packaging products.
 
 Keywords: Montmorillonite, Polypropylene, Nanocomposite, TGME, Compatibility

Oxidative Stress in Xenograft Mouse Model Exposed to Dendrimers Decorated Polydopamine Nanoparticles and Targeted Chemo- and Photothermal Therapy

Polydopamine (PDA)-based nanostructures are used for biomedical purposes. A hybrid drug nanocarrier based on a PDA decorated with polyamidoamine (PAMAM) dendrimers G 3.0 (DG3) followed by a connection with glycol (PEG) moieties, folic acid (FA), and drug doxorubicin (DOX) was used for combined chemo- and photothermal therapy (CT-PTT) of liver cancer. Oxidative stress plays a crucial role in the development of cancer, and PDA seems to have the ability to both donate and accept electrons. We investigated oxidative stress in organs by evaluating oxidative stress markers in vivo. In the liver, the level of reduced glutathione (GSH) was lower and the level of Trolox equivalent antioxidant capacity (TEAC) was higher in the group receiving doxorubicin encapsulated in PDA nanoparticles with phototherapy (PDA@DG3@PEG@FA@DOX + PTT) compared to the control group. The concentration of thiobarbituric acid reactive substances (TBARS) in livers, was higher in the group receiving PDA coated with PAMAM dendrimers and functionalized with PEG and FA (PDA@DG3@PEG@FA) than in other groups. Markers in the brain also showed lower levels of GSH in the PDA@DG3@PEG@FA group than in the control group. Markers of oxidative stress indicated changes in the organs of animals receiving PDA nanoparticles with PAMAM dendrimers functionalized with FA in CT-PTT of liver cancer under in vivo conditions. Our work will provide insights into oxidative stress, which can be an indicator of the toxic potential of PDA nanoparticles and provide new strategies to improve existing therapies.

Advances in the greener synthesis of chromopyrimidine derivatives by a multicomponent tandem oxidation process

A hydrophilic cobalt/copper heterogeneous bimetallic catalyst named mTEG-CS-Co/Cu-Schiff-base/IL was successfully synthesized from chitosan polysaccharide. The new catalyst was investigated and confirmed using various techniques including FT-IR, FE-SEM, EDX-EDS, XRD, TEM, TGA, AFM, NMR and ICP. The catalyst exhibited powerful catalyst activity for the tandem one pot oxidative chromopyrimidine reaction from benzyl alcohols under mild conditions, utilizing air as a clean source in a green protocol. The catalyst was compatible with a wide range of benzyl alcohols, and aldehydes formed in situ, and bis-aldehydes synthesized were condensed with urea/4‑hydroxycumarin to provide favorable products in good yields for all derivatives (14 new derivatives). The presence of tri-ethylene glycol and imidazolium moieties with hydrophilic properties on the mTEG-CS-Co/Cu-Schiff-base/IL nanohybrid provides dispersion of the nanohybrid particles in water, leading to higher catalytic performance. Furthermore, the reaction exhibited several other notable features, including low catalyst loading, the ability to be recycled for up to 6 stages, high atom economy, a simple work procedure, short reaction time, utilization of an environmentally friendly nanohybrid, and the replacement of volatile and organic solvents with water solvent.

Carboxyl-Alkyl Functionalized Conjugated Polyelectrolytes for High Performance Organic Electrochemical Transistors.

Contemporary design principles for organic mixed ionic electronic conductors (OMIECs) are mostly based on the ethylene glycol moiety, which may not be representative of the OMIEC class as a whole. Furthermore, glycolated polymers can be difficult to synthesize and process effectively. As an emerging alternative, we present a series of polythiophenes functionalized with a hybrid carboxyl-alkyl side chain. By variation of the alkyl spacer length, a comprehensive evaluation of both the impact of carboxylic acid functionalization and alkyl spacer length was conducted. COOH-functionalization endows the polymer with preferential intrinsic low-swelling behavior and water processability to yield solvent-resistant conjugated polyelectrolytes while retaining substantial electroactivity in aqueous environments. Advanced in situ techniques, including time-resolved spectroelectrochemistry and Raman spectroscopy, are used to interrogate the materials' microstructure, ionic-electronic coupling, and operational stability in devices. To compare these materials' performance to state-of-the-art technology for the design of OMIECs, we benchmarked the materials and demonstrated significant application potential in both planar and interdigitated organic electrochemical transistors (OECTs). The polythiophene bearing carboxyl-butyl side chains exhibits greater electrochemical performance and faster doping kinetics within the polymer series, with a record-high OECT performance among conjugated polyelectrolytes ([μC*]pOECT = 107 ± 4 F cm-1 V-1 s-1). The results provide an enhanced understanding of structure-property relationships for conjugated polyelectrolytes operating in aqueous media and expand the materials options for future OMIEC development. Further, this work demonstrates the potential for conjugated polymers bearing alkyl-COOH side chains as a path toward robust OMIEC designs that may facilitate further facile (bio)chemical functionalization for a range of (bio)sensing applications.

Novel family of [RuCp(N,N)(P)]+ compounds with simultaneous anticancer and antibacterial activity: Biological evaluation and solution chemistry studies

A family of ten novel ruthenium(II)-cyclopentadienyl organometallics of general formula [Ru(η5-C5H5)(N,N)(PPh2(C6H4COOR)][CF3SO3] (1–10) in which (N,N) = 4,4′-R′-2,2′-bipyridyl (R = –H or –CH2CH2OH; R’ = –H, –CH3, –OCH3, –CH2OH, and –CH2-biotin) was prepared from [Ru(η5-C5H5)(PPh2(C6H4COOH))2Cl]. All compounds were fully characterized by means of several spectroscopic and analytical techniques, and the molecular structures of [Ru(η5-C5H5)(PPh2(C6H4COOH))2Cl], 1, 3 and 4 have been additionally studied by single-crystal X-ray diffraction. The anticancer activity of all compounds was evaluated in sensitive and multidrug-resistant counterpart cell lines from human colorectal cancer (Colo 205 and Colo 320) and non-small cell lung cancer NSCLC (A549, NCI–H460 versus NCI–H460/R) as well. Notably, compounds 6 and 7 (R CH2CH2OH and (N,N) = bipy or Me2bipy, respectively) showed antiproliferative effect against both cell lines with high intrinsic selectivity towards cancer cells. The antibacterial activity of all compounds was also evaluated against both Gram negative and Gram positive strains, and some compounds in the series showed potent antibacterial activity against Staphylococcus aureus strains, including the methicillin-resistant MRSA strains.Solution speciation studies revealed that the complexes bearing the PPh2(C6H4COO−) ligand are neutral at physiological pH (7.4) in contrast with their ethylene glycol derivatives that have a permanent positive charge. While all compounds are lipophilic, the difference in the distribution coefficient for neutral and charged complexes is around one order of magnitude. Complexes 6 and 7 exhibited excellent biological activity and were selected for further studies. Spectrofluorometric methods were used to investigate their interaction with biomolecules such as human serum albumin (HSA) and calf thymus DNA (ct-DNA). For these complexes, binding site II of HSA is a possible binding pocket through non-covalent interactions. The release of ethidium from the DNA adduct by the charged complexes proves their interaction with DNA in contrast to the neutral ones.In conclusion, Ru(II)-cyclopentadienyl complexes with 2,2′-bipyridyl-derivatives and an ethylene glycol moiety tethered to the phenylphosphane co-ligand are very promising from a therapeutic perspective, in particular complexes 6 and 7 that display remarkable antibacterial activity with a high anti-proliferative effect against colon and non-small cell lung cancers, both clinically challenging neoplasias in need of effective solutions.

Synthesis and transport potential study of A2B type double chain amphiphilic architectures

AbstractThe inefficient delivery of drugs having low efficacy to their target sites is significantly hampering the treatment of many diseases and putting enormous pressure on the healthcare system. In this endeavor, the non‐ionic amphiphilic nanotransporters are drawing increasing attention over the past decades. Herein, we report the synthesis of a newer A2B type non‐ionic double chain amphiphilic nanotransporters by using dimethyl 5‐hydroxy isophthalate based central core prepared by propargylation followed by ester hydrolysis. The core was subsequently decorated with hydrophobic alkyl (C8/C20/perfluoro alkylated Cf8) chains via esterification. Monomethoxy polyethylene glycol (mPEG) moiety (Mn: 750/1000) was then incorporated by click chemistry approach to confer hydrophilicity. The aggregation behavior of synthesized non‐ionic amphiphiles in aqueous medium was evaluated by using dynamic light scattering (DLS) and fluorescence spectroscopy. The nanotransport potential of the synthesized amphiphiles was studied by using model hydrophobic guests, that is, the dye Nile red and the drugs nimodipine and curcumin by using ultraviolet–visible (UV/Vis) and fluorescence spectroscopic techniques. Evaluation of the viability of amphiphiles synthesized against HeLa cells showed them to be well tolerated up to the concentration studied. Stimuli responsive release of encapsulated Nile red from the inner core of amphiphile was successfully carried out in the presence of an immobilized enzyme Candida antarctica lipase (Novozym 435). In nutshell, the results obtained from this study may be instrumental in the design and development of promising nanotransporters for biomedical applications.

Site-Selective Functionalized PD-1 Mutant for a Modular Immunological Activity against Cancer Cells.

Targeting immune checkpoints is a well-established strategy in cancer therapy, and antibodies blocking PD-1/PD-L1 interactions to restore the immunological activity against cancer cells have been clinically validated. High-affinity mutants of the PD-1 ectodomain have recently been proposed as an alternative to antibodies to target PD-L1 on cancer cells, shedding new light on this research area. In this dynamic scenario, the PD-1 mutant, here reported, largely expands the chemical space of nonantibody and nonsmall-molecule inhibitor therapeutics that can be used to target cancer cells overexpressing PD-L1 receptors. The polyethylene glycol moieties and the immune response-stimulating carbohydrates, used as site-selective tags, represent the proof of concept for future applications.

Vinyl-addition polynorbornenes with glycerol and diethylene glycol moieties: Synthesis and structure-property study

A set of new norbornene-type monomers containing linear and branched substituents with three C–O–C fragments was synthesized in good yields from commercially available glycerol and diethylene glycol monomethyl ether. Vinyl-addition polymerization of the synthesized monomers was systematically studied, and highly active Pd-catalysts that made it possible to reach quantitative conversions of the monomers were suggested for their polymerization. As a result, robust thin membranes were successfully prepared directly from the polymerization mixtures in the air. Gas separation performance for a wide range of gases was evaluated for the synthesized polymers, and new valuable structure-property relationships were found. More specifically, these membranes display the facilitated transport of CO2 and solubility-controlled hydrocarbon separation selectivity. The increase in the amount of C–O–C fragments in side chains enhances these effects, but only in the case of the linear structure of the substituents. If the structure of side chains becomes branched, the gas permeability is reduced, the facilitated transport of CO2 is minimized, and the polymer becomes more susceptible to plasticization by butane. The facilitated transport of CO2 is due to the specific dipole-quadrupole interaction between CO2 molecules and polymer matrix. For the studied polymers, the contribution of this specific interaction to the solubility of CO2 achieves 64 %. The significant influence of alkyl tails in side chains on gas transport properties was also observed. To achieve better gas separation performance, it is desirable to incorporate short and rigid alkyl tails. Thus, among substituents containing ether moieties, linear oligoethylene glycols with methyl tails seem to be the most promising side-chain substituents for the macromolecular design of CO2-selective polymeric membrane materials. The results obtained were considered along with NMR, TGA, DSC, DMA, and WAXD data.

Lactate dehydrogenase D is a general dehydrogenase for D-2-hydroxyacids and is associated with D-lactic acidosis

Mammalian lactate dehydrogenase D (LDHD) catalyzes the oxidation of D-lactate to pyruvate. LDHD mutations identified in patients with D-lactic acidosis lead to deficient LDHD activity. Here, we perform a systematic biochemical study of mouse LDHD (mLDHD) and determine the crystal structures of mLDHD in FAD-bound form and in complexes with FAD, Mn2+ and a series of substrates or products. We demonstrate that mLDHD is an Mn2+-dependent general dehydrogenase which exhibits catalytic activity for D-lactate and other D-2-hydroxyacids containing hydrophobic moieties, but no activity for their L-isomers or D-2-hydroxyacids containing hydrophilic moieties. The substrate-binding site contains a positively charged pocket to bind the common glycolate moiety and a hydrophobic pocket with some elasticity to bind the varied hydrophobic moieties of substrates. The structural and biochemical data together reveal the molecular basis for the substrate specificity and catalytic mechanism of LDHD, and the functional roles of mutations in the pathogenesis of D-lactic acidosis.

PEGylation versus glycosylation: effect on the thermodynamics and thermostability of crisantaspase

Thermostability is an important and desired feature of therapeutic proteins and is critical for the success or failure of protein drugs development. It can be increased by PEGylation—binding of poly(ethylene glycol) moieties—or glycosylation—post-translational modification to add glycans. Here, the thermostability and thermodynamic parameters of native, PEGylated, and glycosylated versions of the antileukemic enzyme crisantaspase were investigated. First-order kinetics was found to describe the irreversible deactivation process. Activation energy of the enzyme-catalyzed reaction (E*) was estimated for native, PEGylated, and glycosylated enzyme (10.2, 14.8, and 18.8 kJ mol−1 respectively). Half-life decreased progressively with increasing temperature, and longer half-life was observed for PEG-crisantaspase (87.74 min) at 50 °C compared to the native form (9.79 min). The activation energy of denaturation of PEG-crisantaspase (307.1 kJ mol−1) was higher than for crisantaspase (218.1 kJ mol−1) and Glyco-crisantaspase (120.0 kJ mol−1), which means that more energy is required to overcome the energy barrier of the unfolding process. According to our results, PEG-crisantaspase is more thermostable than its native form, while Glyco-crisantaspase is more thermosensitive.

Synthesis and Functionalization of Unsymmetrical Terbium(III) Bis-Phthalocyaninates, Promising Components of Hybrid Magnetic Materials

A new unsymmetrical terbium bis-Phthalocyaninate Tb(A7B) with one terminal aliphatic OH group was obtained by template cross-condensation of diethoxyphthalonitrile (A) and phthalonitrile (B) functionalized with diethylene glycol moiety. The subsequent functionalization of the complex included the successive replacement of this OH group by the iodide and thioacetate substituents. The synthesized complexes can act as components of hybrid materials upon immobilization on surfaces of various nature.

Recent Developments in the Design of New Water-Soluble Boron Dipyrromethenes and Their Applications: An Updated Review.

Boron-dipyrromethene (BODIPY) and its derivatives play an important role in the area of organic fluorophore chemistry. Recently, the water-soluble boron-dipyrromethene dyes have increasingly received interest. The structural modification of the BODIPY core by incorporating different neutral and ionic hydrophilic groups makes it water-soluble. The important hydrophilic groups, such as quaternary ammonium, sulfonate, oligoethylene glycol, dicarboxylic acid, and sugar moieties significantly increase the solubility of these dyes in water while preserving their photophysical properties. As a result, these fluorescent dyes are utilized in aqueous systems for applications such as chemosensors, cell imaging, anticancer, biolabeling, biomedicine, metal ion detection, and photodynamic treatment. This review covers the most current developments in the design and synthesis of water-soluble BODIPY derivatives and their wide applications since 2014.

Direct and Indirect DNP NMR Uncovers the Interplay of Surfactants with Their Mesoporous Host Material

Two different mesoporous silica materials (SBA-15 and MCM 41) were impregnated with four different, commercially available surfactants, namely, E5, PEG 200, C10E6, and Triton X-100. Differential scanning calorimetry was employed to confirm the confinement of the surfactants in the pores of their host materials. Dynamic nuclear polarization enhanced solid state 13C magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectra were recorded for these materials, showing that both the direct as well as the indirect polarization transfer pathways are active for the carbons of the polyethylene glycol moieties of the surfactants. The presence of the indirect polarization pathway implies the presence of molecular motion with correlation times faster than the inverse Larmor frequency of the observed signals. The intensities of the signals were determined, and an approach based on relative intensities was employed to ensure comparability throughout the samples. From these data, the interactions of the surfactants with the pore walls could be determined. Additionally, a model describing the surfactants’ arrangement in the pores was developed. It was concluded that all carbons of the hydrophilic surfactants, E5 and PEG 200, interact with the silica walls in a similar fashion, leading to similar polarization transfer pathway patterns for all observed signals. For the amphiphilic surfactants C10E6 and Triton X-100, the terminal hydroxyl group mediates the majority of the interactions with the pore walls and the polarizing agent.