bluuebunny/crossref_metadata_2025_split huggingface dataset:
Self‐promoted Controlled Ring‐opening Polymerization via Side Chain‐mediated Proton Transfer for the Synthesis of Tertiary Amine‐pendant Polypeptoids
Authors: Liao Mingzhen , Yao Yao , Gan Kunyu , Su Xianghua , Zhao Ning , Zuckermann Ronald N. , Xuan Sunting , Zhang Zhengbiao 
Published: October 2024

AbstractProton transfer is essential in virtually all biochemical processes, with enzymes facilitating this transfer by optimizing the proximity and orientation of reactants through site‐specific hydrogen bonds. Proton transfer is also crucial in the rate‐determining step for the ring‐opening polymerization of N‐carboxyanhydrides (NCAs), widely used to prepare various peptidomimetic materials. This study utilizes side chain‐assisted strategy to accelerate the rate of chain propagation by using NCAs with tertiary amine pendants. This moiety enables hydrogen bond formation between the incoming NCA and the polymer amino growing end. The tertiary amine side chain of the NCA forms a proton shuttle, via a less constrained transition state, to facilitate the proton transfer process. Moreover, the tertiary amine side chains enable the precipitation of NCA monomers through in situ protonation during the monomer synthesis. This greatly facilitates the synthesis of these unreported monomers, allowing the direct controlled synthesis of tertiary amine‐pendant polypeptoids. This side chain‐promoted polymerization has rarely been reported. Additionally, the tertiary amine side chains, as widely used functional groups, endow the polymers with unique properties including pH‐ and thermo‐responsiveness, tunable pKas, and siRNA transfection capability. The self‐promoted synthesis, facile monomer preparation, and attractive properties make tertiary amine‐pendant polypeptoids promising materials for various applications.
π‐Complexes Derived from Non‐classical Diboriranes: Side‐on vs. End‐on Carbonylative Ring Expansion
Authors: Grewelinger Philipp , Präsang Carsten , Zimmer Michael , Morgenstern Bernd , Scheschkewitz David 
Published: October 2024

AbstractUnlike cyclopropanes, the analogous B2C species (diboriranes) tend to adopt non‐classical Hückel‐aromatic structures with bridging moieties R between the boron atoms. The coordination of the thus generated cyclic 2e− π‐system to transition metals is completely unexplored. We here report that complexation of non‐classical diboriranes cyclo‐μ‐RB2Dur2CPh (R=H, SnMe3; Dur=2,3,5,6‐tetramethylphenyl) to Fe(CO)3 fragments allows for the carbonylative ring expansion of the B2C ring to either four‐ or five‐membered rings depending on the nature of the BRB 3‐center‐2‐electron bond (3c2e): The H‐bridged diborirane (R=H) initially reacts with Fe2(CO)9 to the allylic π‐complex with an agostic BH/Fe interaction. Subsequent formal hydroboration of CO from excess Fe2(CO)9 results in the side‐on ring expansion under formation of a five‐membered B2C2O ring, coordinated to the Fe(CO)3 moiety. In contrast, in case of the stannyl‐bridged diborirane (R=SnMe3) under the same conditions, CO is added end‐on to the B−B bond with the carbon terminus formally inserting into the B2Sn 3c2e‐bond. The two carbonylative ring expansion products can also be described as nido and closo clusters, respectively, according to the Wade‐Mingos rules.
Novel Co2+ and Cd2+ Complexes Derived From a New N‐Donor Pyridyl‐Functionalized Thiophosphoric Triamide Ligand: Structural Investigation, DNA/COVID‐19/Monkeypox Molecular Docking, and Biological Assays
Authors: Albobaledi Zeinab , Tarahhomi Atekeh , Khaleghian Ali , van der Lee Arie , Excoffier Grégory 
Published: October 2024

ABSTRACTA thiophosphoric triamide (SPT) ligand P(S)[NH‐2Py]3 was synthesized and utilized as a ligand to make novel binuclear and mononuclear Co2+ and Cd2+ complexes. The compounds are the first examples of discrete chelate SPT complexes with a [N]3P(S)‐based backbone in which the SPT acts as a flexible tridentate N,N,N‐donor or N,N,O‐donor ligand. The metal cation features a hexacoordinate environment M(N)3(Cl)3/M(N)4(O)2 adopting a distorted octahedral geometry. Hirshfeld surface analysis affirms that the pyridinyl nitrogen is a more dominant H‐bond acceptor than the thiophosphoryl sulfur atom. The inhibitory activity against the MDA‐MB‐231 cancer cell line in vitro indicated a good inhibitory effect for all compounds. The mononuclear Co2+ complex showed a stronger inhibitory activity against cancer cells than other studied compounds with an IC50 of 62 ± 1.4 nM. Antioxidant and antihemolytic activity of the compounds showed appreciable performance with the highest activities for the Cd2+ complex. A computational DNA binding study by molecular docking indicated a good affinity of the compounds with the DNA receptor by a mixed mode of interactions. Docking was also performed on SARS‐CoV‐2 and monkeypox (Mpox), resulting in binding energies (−5.5 to −8.9 kcal/mol) that are competitive with current effective drugs.
Pyrrolopyrimidinehydrazide‐2‐chlorobenzaldehyde Metal Complexes: Synthesis, Characterization, and Extraordinary Exploration Through in Vitro, in Vivo Cytotoxicity, and Cutting‐Edge Computational Analyses
Authors: Bagul Abhay D. , Gaikwad Digambar D. , Tufail Aisha , Sangshetti Jaiprakash N. , Damale Manoj G. , Dubey Amit 
Published: October 2024

ABSTRACTThis study reports the successful synthesis and characterization of five novel metal complexes (1–5) derived from the pyrrolopyrimidinehydrazide‐2‐chlorobenzaldehyde ligand, HPPHoCBA (L). The metal complexes demonstrated non‐electrolytic behavior and distinct geometries, as confirmed through comprehensive physicochemical analyses. Importantly, the synthesized complexes exhibited significantly enhanced antimicrobial, antioxidant, and cytotoxic activities compared to the ligand HPPHoCBA (L). Molecular docking studies revealed superior binding affinities of Pd(II) (1) and Cd(II) (4) complexes, which were further substantiated by pharmacophore modeling. Additionally, density functional theory (DFT) and molecular electrostatic potential (MEP) analyses provided insights into the stability and reactivity of these complexes, suggesting their potential in future therapeutic applications. These findings underscore the potential biomedical and industrial applications of the synthesized metal complexes.
CsPbX3 Nanocrystal Incorporating Transition Metal Cocatalyst for Photocatalytic Organic Transformation by Single Electron Transfer
Authors: Guo Zhifen , Cheng Zihan , Xing Hongmei , Li Xinyu , Sun Yelan , Yang Hui , Jiao Wenmei , Du Pan , Chen Dashu 
Published: October 2024

ABSTRACTThe construction of composite photocatalysts is a promising strategy for improving the overall catalytic efficiency in organic photochemical transformation. In this study, we synthesize a series of inorganic metal perovskite CsPbX3 (X = Cl, Br, I) nanocrystals (NCs) with excellent chemical stability and wide‐range visible‐light absorption. The Pd cocatalyst is then induced to the surfaces of CsPbX3 fabricating Pd/CsPbX3 composites via visible‐light reduction method. Photoelectrochemical measurements show the introduction of Pd cocatalyst promotes efficiently the charge separation and transfer of CsPbX3. The prepared Pd/CsPbX3 composites exhibit remarkable photocatalytic efficiency in visible‐light‐induced C–C cross‐coupling reaction. The reaction is characterized by mild reaction conditions, good recyclability, and high yield from a broad variety of substrates. Mechanism investigations show the reaction relies on the synergy of CsPbX3 photocatalysis and Pd catalysis. The valence band of CsPbX3 oxidizes the phenylboronic acid into active radical species via single electron transfer. On another hand, Pd(0) as active sites occurs oxidative addition with aryl halides for achieving the C–C cross‐coupling reaction. This study displays a feasible approach for the introduction of Pd catalyst in CsPbX3 to achieve the photocatalytic organic transformation via photoinduced electron transfer.
Nano‐Multiactive Sites Pd/PdO/CuO/PdCu3 Formed In Situ on the Surface Hetero‐Organometallic Pd(II)/Cu(II) Nanosheet: Investigation on the Formation of Active Sites, Synergistic, and Catalytic Activity
Authors: Li Naming , Huang Dongmei , Li Tiesheng , Liu Minghua , Wu Yangjie 
Published: October 2024

ABSTRACTExploring the relationship between the structure of active site and the activity in molecular level and investigating the reason for deactivation are extremely important in designing the highly active catalyst. In this paper, new self‐assembly Schiff‐base Pd/Cu nanosheets supported on the surface of graphene oxide (GO) (called as GO@Hpmaba‐Pd/Cu) were fabricated and characterized. Among them, GO@Hpmaba‐Pd0.2/Cu0.8 exhibited a high activity with a TOF value of up to 95,357 h−1 and substrate suitability in Suzuki cross‐coupling reaction. GO@Hpmaba‐Pd0.2/Cu0.8 could be reused at least 13 times. GO@Hpmaba‐Pd0.2/Cu0.8 was a heterogeneous catalyst and the catalysis occurred on the surface. The truly active sites included Pd/PdO/CuO/PdCu3 formed in situ on the surface of the hetero‐organometallic Pd/Cu nanosheet during catalysis. The synergistic effects among these active sites could be described as that the electrons transferred from GO to CuO (PdO) or to Pd via ligand (Hpmaba) and subsequently electrons transferred from CuO (PdO) to Pd. These made more electron negative palladium, enhancing the oxidation addition between palladium and aryl halide and prompting the activity. The deactivation of catalyst was mainly caused by some destroyed organometallic in the nanosheet, residues adsorbed on catalytic surface, loss of active Pd due to the leaching with increase of recycling, and the aggregation of active metals.
Preparation of grafted starch‐based cationic flocculants and its removal of reactive and disperse dyes
Authors: Zhao Xiaoxu , Zhang Rui , Cao Shuchen , Chang Na , Zhang Hao 
Published: October 2024

AbstractIn this paper, a starch‐based flocculant (ADSt) with medium and low temperature solubility and enhanced flocculation effect was synthesized using corn starch, acrylamide, and dimethyldiallyl ammonium chloride as main materials by the ethanol‐alkali method and grafting method. The main mechanism of ADSt's flocculation was electrical neutralization and bridging. The flocculation performance of ADSt was verified by using it along with polymeric aluminum chloride (PAC) as coagulant/flocculant, dispersible dye (dispersible yellow RGFL), and reactive dye (active trimeric blue KN‐G) to simulate dye wastewater. For the dispersed yellow water sample and active emerald blue water sample, the dosage of PAC was 40 and 35 mg/L respectively. When the dosage of ADSt was 10 mg/L with a dye content of 100 mg/L, the decolorization rates for both dyes reached up to 96.2% and 94.4% respectively. The properties of the flocs such as size and two‐dimensional fractal structure were described. The prepared ADSt maintained a good flocculation effect in the pH range of 5–9 due to its excellent water solubility achieved through the ethanol‐alkali preparation process, where its solubility reached 86.7% at 30°C. Overall, the preparation process for ADSt is simple, cost‐effective, while providing an effective solution for treating printing and dyeing wastewater.
Waterborne novolac epoxy‐based thermal resistant and fire‐retardant thermal insulation coatings
Authors: Zhang Lei , Pei Shi‐Bo , Zhang Meng , Meng Xu , Ren Qiang , Wang Chen‐Yi 
Published: October 2024

AbstractWaterborne novolac epoxy based thermal resistant and fire‐retardant thermal insulation coatings were developed in this work. Novolac (phenolic) epoxy emulsion (PEE) was prepared by the phase inversion method based on formulation optimization by orthogonal array testing. The prepared emulsions have similar particle size, viscosity, and stability to commercial bisphenol a glycidyl ether epoxy emulsion (PZ). DSC results showed that the varnish film based on PEE had a higher glass transition temperature and initial thermal decomposition temperature compared with PZ cured by the same curing agent. Waterborne thermal insulation coating with PEE and PZ as binders and hollow glass microspheres (HGMs) as thermal insulation fillers were studied. The results indicated that the thermal conductivity of the coating decreased with an increase in HGMs content. Specifically, the thermal conductivity of the PEE coating containing 20 wt% HGMs is as low as 0.093 W/(m·K). It reduces the exterior temperature of the hot tank from approximately 200 °C to approximately 106 °C. Furthermore, the HGMs/PEE waterborne thermal insulation coating exhibits good thermal stability and flame retardance.
Pesticide delivery microcapsule based on maleic anhydride‐functionalized cellulose nanocrystals‐stabilized pickering emulsion
Authors: Wu Chao , Li Yong‐jiang , Ding Jia‐wei , Jiang Hui , Su Hui‐fen , Liu Yue , Gao Tian‐yu , Li De‐qiang , Li Jun 
Published: October 2024

AbstractThe efficient use of pesticides is conducive to the harmonious coexistence of humans and nature, and pesticide transport carriers can enhance the utilization value of pesticides. However, design flaws in many pesticide carriers have resulted in numerous environmental and toxicity problems. Therefore, this paper proposed a method for synthesizing pesticide microcapsules using Pickering emulsion templates stabilized by maleic anhydride‐functionalized cellulose nanocrystals‐g‐poly (methyl methacrylate) (MACNCs‐g‐MMA), viz., simple radical polymerization of maleic anhydride‐functionalized cellulose nanocrystals with methyl methacrylate in Pickering emulsion. The structure and morphology of microcapsules were characterized via the FT‐IR, XRD, TG‐DTG, and SEM techniques. The imidacloprid‐loaded MACNCs‐g‐MMA (IMI@MACNCs‐g‐MMA) presented a high encapsulation efficiency (~94.13%) and drug loading efficiency (~24.00%). The release behavior was affected by temperature, viz., higher temperature promoted the release of IMI. Regarding the spread and retention on the leaf surface, the IMI@MACNCs‐g‐MMA demonstrated significant advantages over commercial IMI water‐dispersible granules (CG) (36.9° vs. 104.9° for contact angle, 14.3 vs. 30.0 mg cm−2 for retention). This study provides a promising pesticide formula for sustainable agriculture.
An Update on the Conservation Status Assessment of two Endangered Freshwater Mussel Species in Bavaria, Germany
Authors: Dobler Andreas H. , Hoos Philipp , Geist Juergen 
Published: October 2024

ABSTRACTThe two highly endangered European mussel species Margaritifera margaritifera and Unio crassus are target species of conservation. Based on a recently completed systematic state‐wide monitoring of each 22 M. margaritifera and 22 U. crassus streams in Bavaria, Germany, we present an update on population trends, conservation status, habitat quality and threats for both species. Populations status and habitat quality varied strongly between M. margaritifera and U. crassus streams, but there was also great variability within each of those groups. The population decline of M. margaritifera has continued, albeit higher proportions of juveniles originating from artificial breeding programmes have been established in some streams. Habitat quality often did not match known requirements as evident from poor stream bed quality, lack of hosts and elevated nutrient levels. In contrast, U. crassus populations showed a better status, with an increase in population size over all sampled streams. Successful recruitment was indicated by high proportions of juveniles. However, no mussels older than 16 years were found, probably due to predation and structural stream maintenance measures. Climate change effects, such as extreme droughts, affected both species. This study demonstrates different needs in conservation management for both species. Although mitigation of drought effects is commonly needed for both species, tackling host fish management and direct threats such as predation should be prioritized in U. crassus, whereas restoration of prime habitat quality and intact catchments is key to enable natural recruitment and sustainable populations of M. margaritifera.
The archaeology of eastern Lutruwita (Tasmania)
Authors: Cosgrove Richard , Webb John , Garvey Jillian , Theys Jeff , Jones Rhys 
Published: October 2024

ABSTRACTFifty years have passed since the first systematic archaeological surveys and excavations were conducted in Lutruwita (Tasmania). Despite numerous Late Pleistocene archaeological discoveries in the southwest region, no indisputable pre‐Holocene sites have been found in eastern Tasmania. This profound difference raises questions about how Aboriginal people utilised the Lutruwita landscape; first as a projecting peninsula into the Southern Ocean and then as an island cut off by rising seas c.14000 years ago.To examine the difference between east and west further, legacy data excavated by one of us (RJ) in 1964 at the Oatlands OL1 site and stored at the Tasmanian Museum and Art Gallery (TMAG) has been analysed. The results of pXRF chemical analysis of artefact raw material, radiocarbon dating and studies of faunal remains have produced information that highlights the Holocene interaction between people in eastern Lutruwita. Despite the current lack of Late Pleistocene evidence from eastern Lutruwita, this pattern appears to be different from land use models for Late Pleistocene southwestern Lutruwita. With new information from the OL1 rock shelter site we can now contrast the Late Pleistocene hunting economics with the exceptionally well‐preserved faunal remains found in the Holocene site, OL1.
Synthesis and characterization of aniline‐based azo molecules: In vitro pharmacological and emission studies
Authors: Shakuntala R. B. , Keshavayya J. , Mussuvir pasha K. M. , Pampapathi S. 
Published: October 2024

AbstractThe present work involves the synthesis of novel dispersed mono‐azo dyes using different coupling components and 2‐methoxy‐5‐nitro aniline as amine through a simple and convenient diazo‐coupling method. The structures of the newly synthesized mono azo dyes were confirmed by using various spectral techniques such as 1H NMR, Fourier transform infrared, and high‐resolution mass spectrometry. At room temperature, the electronic absorption spectra and fluorescence spectra of the synthesized mono azo dyes were recorded with different solvents. The global reactive parameters for the synthesized azo molecules were evaluated by performing density functional theory through the 6–311++G (d, p) basis set. The anti‐microbial activities for the synthesized azo compounds were carried out, and the compounds G1 and G2 exhibited good antibacterial and anti‐fungal activities. The in silico molecular docking studies of the azo molecules revealed that all the compounds exhibited extraordinary binding affinity as that of the standard drug. Further, the anti‐tuberculosis study against the Mycobacterium tuberculosis for the synthesized azo dyes was evaluated, and from the results, it was revealed that the compound G4 showed good sensitivity among the other synthesized azo compounds.
Nitrogen and Sulfur Co‐Doped Carbon Quantum Dots as Fluorescent Nanosensors for Determination of Two Tetracycline Antibiotics in Dosage Forms and Human Plasma: Compliance With Greenness Metrics
Authors: El‐libeshy Aya A. , Abdel‐Megied Ahmed M. , Rashed Noha Salem , Nasr Zeinab Adel , Magdy Galal 
Published: October 2024

ABSTRACTIn this study, a novel, sensitive, and cost‐effective spectrofluorimetric approach was established for the estimation of two important tetracycline antibiotics, tetracycline and doxycycline, without any pre‐treatment procedures or harsh reaction conditions, for the first time. The proposed methodology is based on the quantitative quenching effect of each tetracycline and doxycycline on the native fluorescence of nitrogen and sulfur co‐doped carbon quantum dots (NS‐CQDs). A simple and ultrafast approach was applied to synthesize NS‐CQDs using thiosemicarbazide and citric acid as starting materials after incubation in a microwave for only 1 min. Utilizing an excitation wavelength of 360 nm, NS‐CQDs showed maximum emission peak at 430 nm. Calibration curves revealed excellent linearity within the ranges of 1.0–10.0 and 0.8–12.0 μg/mL with detection limits of 0.20 and 0.09 μg/mL for tetracycline and doxycycline, respectively. Due to the method's high sensitivity and selectivity, the proposed approach was applied for the determination of the studied drugs in their capsules and human plasma samples with high %recoveries. The developed approach was validated according to ICHQ2(R2) guidelines. GAPI and AGREE metric tools were used to verify the method's greenness and eco‐friendliness, suggesting its use as a green substitute for the analysis of the studied drugs.
Posttranslational modifications in retinal degeneration diseases: An update on the molecular basis and treatment
Authors: Yao Ke , Mou Qianxue , Jiang Zhen , Zhao Yin 
Published: October 2024

AbstractNoninherited diseases and age‐associated vision loss are often associated with retinal degeneration. The retina is a postmitotic neural tissue lacking endogenous regeneration capacity. Therefore, understanding the mechanism of retinal degeneration in diseases is pivotal. Posttranslational modifications (PTMs) determine protein function during physiological and pathological processes, including signal transduction, protein localization, and protein activation. Advanced detection technologies have revealed over 400 different PTMs including acetylation, methylation, phosphorylation, ubiquitination and SUMOylation. Here, we discuss PTMs in retinal degeneration diseases to aid in our understanding of their molecular basis and suggest potential future clinical treatment.
General strategies for IgG‐like bispecific antibody purification
Authors: Li Yifeng 
Published: October 2024

AbstractBispecific antibodies (bsAbs) can simultaneously bind two different antigens or epitopes. Their dual‐targeting capability enables novel mechanisms of action, gaining therapeutic advantages over conventional monospecific mAbs. In recent years, the number of bsAbs grows rapidly and bsAbs under development are available in diverse formats. In particular, Fc‐containing IgG‐like bsAbs, which represent the major group, can be constructed in asymmetric or symmetric format. For asymmetric ones, whose assembly requires multiple distinct chains, although numerous strategies have been developed to promote desired chain pairing, product‐related variants such as free chains, half molecules and mispaired species are usually present at various levels. For symmetric ones, increased level of aggregates and truncating variants is often associated with their production. In general, bsAbs pose greater challenges to the downstream team than regular mAbs. In the past few years, our team successfully developed the downstream process for over 70 bsAbs in greater than 30 different formats and accumulated substantial experience. This review introduces general strategies that we have used while purifying these challenging molecules.