Product Structure Research Articles

Solvent-Free Enzymatic Synthesis of Ethyl 3-Oxobutyrate Derivative: Characterization and Optimization of Reaction Condition.

It was first found that porcine pancreatic lipase (PPL) could catalyze the Knoevenagel condensation of aromatic aldehydes and ethyl acetoacetate under solvent-free conditions in this paper. Under solvent-free conditions, the highest yield of PPL catalytic reaction was 99.38%, and the Z/E selectivity of the product was 3.93. In addition, the reaction conditions were optimized, and the factors affecting the product structure were studied.

Modular Synthesis of [6,6]‐Oxaspirolactones Enabled by Palladium‐Catalyzed Carbonylative Spirolactonization

AbstractAn expedient and efficient carbonylative protocol proceeded via palladium‐catalyzed tandem cyclic ketonization and carbonylative spirolactonization has been developed. This carbonylation reaction is compatible with a wide range of hydroxyalkyl ketone tethered benzyl chlorides bearing different functional groups and can be proceeded under comericially available Pd2(dba)3/BINAP catalyst system, providing a straithfowrd and practical approach to a broad range of [6,6]‐oxaspirolactones. The synthesized [6,6]‐oxaspirolactones are commonly found as core structures in natural products and can potentially serve as C2‐symmetric ligand synthons.

Spatio-Temporal Evolution and Drivers of Carbon Emission Efficiency in China’s Iron and Steel Industry

Improving the carbon emission efficiency (CEE) of the iron and steel industry (ISI) is crucial for China to achieve the goal of carbon peak and carbon neutrality. This study employed the undesirable SBM and Dagum Gini coefficient to measure the ISI’s CEE and analyzed the spatial heterogeneity among three regions of China. This study also used the Tobit model to clarify the influencing factors. The conclusions show that (1) the CEE in eastern provinces is the highest, the central ones rank second, while the western ones rank the worst; the promoting effect of Technical Change is greater than that of Efficiency Change. (2) ISI’s CEE shows a positive spatial correlation and an apparent spatial heterogeneity. The CEE gap between the regions contributes most to the CEE difference among provinces. The regional CEE gap within the western region is the largest, with a maximum difference of 0.520 in the Dagum Gini coefficient. Furthermore, the total CEE gap shows a narrowing trend from 2009 to 2020, with the Dagum Gini coefficient decreasing from 0.414 in 2009 to 0.357 in 2020. (3) Industrial structure, enterprise scale, foreign direct investment, and technology level positively correlate with ISI’s CEE; the marginal impacts are 0.6711, 0.1203, 0.0572, and 3.5191, respectively. While energy intensity, environmental regulation, and product structure negatively correlate with it, the marginal impacts are 0.0178, 1.4673, and 0.2452, respectively.

Polynomial decompositions with invariance and positivity inspired by tensors

We present a framework to decompose real multivariate polynomials while preserving invariance and positivity. This framework has been recently introduced for tensor decompositions, in particular for quantum many-body systems. Here we transfer results about decomposition structures, invariance under permutations of variables, positivity, rank inequalities and separations, approximations, and undecidability to real polynomials. Specifically, we define invariant decompositions of polynomials, and characterize which polynomials admit such decompositions. We then include positivity: We define invariant separable and sum-of-squares decompositions, and characterize the polynomials similarly. We provide inequalities and separations between the ranks of the decompositions, and show that the separations are not robust with respect to approximations. For cyclically invariant decompositions, we show that it is undecidable whether the polynomial is nonnegative or sum-of-squares for all system sizes. Our framework is different from existing approaches for polynomial decompositions, since it covers symmetry and positivity combined, in a clean and uniform way. Also, our work sheds new light on polynomials by putting them on an equal footing with tensors, and opens the door to extending this framework to other tensor product structures.

Enantioselective synthesis of chiral amides by carbene insertion into amide N–H bond

Chiral amides are important structure in many natural products and pharmaceuticals, yet their efficient synthesis from simple amide feedstock remains challenge due to its weak Lewis basicity. Herein, we describe our study of the enantioselective synthesis of chiral amides by N-alkylation of primary amides taking advantage of an achiral rhodium and chiral squaramide co-catalyzed carbene N–H insertion reaction. This method features mild condition, rapid reaction rate (in all cases 1 min) and a wide substrate scope with high yield and excellent enantioselectivity. Further product transformations show the synthetic potential of this reaction. Mechanistic studies reveal that the non-covalent interactions between the catalyst and reaction intermediate play a critical role in enantiocontrol.

The Adsorption Ability of Cibacron Red Dye from Aqueous Solution Using Copper Oxide Nanoparticles

يصف هذا البحث الإنتاج الصديق للبيئة لجسيمات النحاس النانوية باستخدام مستخلص نبات الجرجير والحرق عند درجة حرارة 400 درجة مئوية لمدة 3 ساعات. تم استخدام SEM و TEM لتحليل حجم الجسيمات النانوية المحضرة. تم استخدام حيود الأشعة السينية لتحديد الهيكل البلوري. كشف التحليل الطيفي للأشعة السينية المشتتة للطاقة لهيكل المنتج الذي تم إنشاؤه عن مكونات النحاس والأكسجين فقط ، مما يدل على نقاء المادة المحضرة. استخدمت المادة النانوية المحضرة CuO NPs في امتزاز صبغة Cibacron الحمراء. في 35 دقيقة من زمن الاتزان ، لوحظ امتزاز أسرع لصبغة Cibacron الحمراء على الجسيمات النانوية CuO . كان نموذجا Freundlich و pseudo-second ذات قيم R2 أكثر من 0.9785 و 0.999 على التوالي ، الأكثر فاعلية في وصف عملية الامتزاز. تم حساب المعلمات ΔG, ΔH, ΔS. يمكن الاستنتاج أن CuO NPs هي سطح ممتز فعال لصبغة Cibacron الحمراء.

A Q-Learning Based Hybrid Meta-Heuristic for Integrated Scheduling of Disassembly and Reprocessing Processes Considering Product Structures and Stochasticity

A Q-Learning Based Hybrid Meta-Heuristic for Integrated Scheduling of Disassembly and Reprocessing Processes Considering Product Structures and Stochasticity

Space-time CutFEM on overlapping meshes II: simple discontinuous mesh evolution

We present a cut finite element method for the heat equation on two overlapping meshes: a stationary background mesh and an overlapping mesh that evolves inside/“on top” of it. Here the overlapping mesh is prescribed by a simple discontinuous evolution, meaning that its location, size, and shape as functions of time are discontinuous and piecewise constant. For the discrete function space, we use continuous Galerkin in space and discontinuous Galerkin in time, with the addition of a discontinuity on the boundary between the two meshes. The finite element formulation is based on Nitsche’s method. The simple discontinuous mesh evolution results in a space-time discretization with a slabwise product structure between space and time which allows for existing analysis methodologies to be applied with only minor modifications. We follow the analysis methodology presented by Eriksson and Johnson (SIAM J Numer Anal 28(1):43–77, 1991; SIAM J Numer Anal 32(3):706–740, 1995). The greatest modification is the introduction of a Ritz-like “shift operator” that is used to obtain the discrete strong stability needed for the error analysis. The shift operator generalizes the original analysis to some methods for which the discrete subspace at one time does not lie in the space of the stiffness form at the subsequent time. The error analysis consists of an a priori error estimate that is of optimal order with respect to both time step and mesh size. We also present numerical results for a problem in one spatial dimension that verify the analytic error convergence orders.

Replacement of Loops at the Entrance of the Active Pocket of Streptococcus thermophilus 4,6-α-Glucanotransferase Changes Its Catalytic Activity and Product Specificity.

To explore the roles of loops around active pocket in the reuteran type 4,6-α-glucanotransferase (StGtfB) from S. thermophilus, they were individually or simultaneously replaced with those of an isomalto/maltopolysaccharides type 4,6-α-glucanotransferase from L. reuteri. StGtfB with the replaced loops A1, A2 (A1A2) and A1, A2, B (A1A2B), respectively, showed 1.41- and 0.83-fold activities of StGtfB. Two mutants reduced crystallinity and increased starch disorder at 2, 4, and 8 U/g more than StGtfB and increased DP ≤ 5 short branches of starch by 38.01% at 2 U/g, much more than StGtfB by 4.24%. A1A2B modified starches had the lowest retrogradation over 14 days. A1A2 modified starches had the highest percentage of slowly digestible fractions, ranging from 40.32% to 43.34%. StGtfB and its mutants bind substrates by hydrogen bonding and van der Waals forces at their nonidentical amino acid residues, suggesting that loop replacement leads to a different conformation and changes activity and product structure.

Locally acting dermatology drug products: Pharmaco-analytic considerations for bioequivalence

Bioequivalence determinations for locally acting dermatology drug products rely on assessing product sameness thru physicochemical composition and structure comparison, comparing the concentration of the active ingredient at the putative site of action, or comparing the clinical performance of the test (would-be generic) and reference products. Topical product action on cutaneous disease may be confounded by the action of excipients and are also subject to the inherent variability of how product may interact with the skin, including thermodynamic factors such as evaporation, spreadability, and interaction with the local environment such as heat and light and skin moisture.

A top-down lashing bridge collaborative design method

ABSTRACT The short detailed design cycle of lashing bridges on container ships needs to ensure that various designs have different requirements at multiple locations on the ship, making the design methodology for complex products challenging. Currently, research on the design methodology of lashing bridges lacks in-depth investigation into detailed design aspects. This work addressed research gaps through a top-down collaborative design approach and analysed the principles of propagating design changes in computer-aided design (CAD), as well as proposed a design methodology consisting of four core steps, namely, skeleton decomposition, feature aggregation, detailed design and product structure (PS) expansion. The effectiveness of this methodology was validated through practical design examples and specific variant design instances of a certain type of container ship. The validation demonstrated that the proposed design methodology, in contrast to traditional three-dimensional design methods, supported design process reuse and significantly improved design efficiency in complex product designs.

Indentification of coal-origin structural units by multi-step pyrolysis through Py-GC/MS and by DFT calculation

Most of the existing structural models of coal macromolecules are based on indirect characterization, which cannot reflect the real product structure of coal pyrolysis. This study focuses on the construction of the real structural units of de-ashed Shendong coal (RD) and its vitrinite (VD) and inertinite (ID). Two pyrolysis modes of fast pyrolysis–gas chromatography/mass spectrometry (Py-GC/MS), Thermogravimetry (TG), Fourier transform infrared (FTIR) as well as rapid infrared heating (RIH) were used to obtain the pyrolysis properties and product composition distributions of each coal. A strategy for structural unit construction of coal, termed “Molecular Reorganization”, is introduced to ensure that the original structure of the coal can be reproduced. Macromolecules produced by multi-step pyrolysis in the low-temperature region were used to assemble the real structural units of coal. The pyrolysis pathways of the oxygenated compounds in the constructed molecular unit models of RD-C70H50O9N, ID-C101H62O13N2, and VD-C71H43O9N were analyzed by density functional theory (DFT). The results showed that the reaction energy for the pyrolysis of ID fragments to phenol was higher, with fragments 1 and 2 being −4212.98 kJ/mol and −2190.83 kJ/mol, respectively.

Preparation and Hydration Properties of Sodium Silicate-Activated Municipal Solid Waste Incineration Bottom Ash Composite Ground-Granulated Blast Furnace Slag Cementitious Materials.

The production of municipal solid waste incineration bottom ash (MSWIBA) is substantial and has the potential to replace cement, despite challenges such as complex composition, uneven particle size distribution, and low reactivity. This paper employs sodium silicate activation of MSWIBA composite Ground-granulated Blast Furnace slag (GGBS) to improve the reactivity in preparing composite cementitious materials. It explores the hydration performance of the composite cementitious materials using isothermal calorimetric analysis, Fourier-transform infrared (FTIR) spectroscopy, XRD physical diffraction analysis, and SEM tests. SEM tests were used to explore the hydration properties of the composite gelling. The results show that with an increase in MSWIBA doping, the porosity between the materials increased, the degree of hydration decreased, and the compressive strength decreased. When the sodium silicate concentration increased from 25% to 35%, excessive alkaline material occurred, impacting the alkaline effect. This inhibited particle hydration, leading to a decrease in the degree of hydration and, consequently, the compressive strength. The exothermic process of hydration can be divided into five main stages; quartz and calcite did not fully participate in the hydration reaction, while aluminum did. The vibrational peaks of Si-O-Ti (T = Si and Al) were present in the material. The vibrational peaks of XRD, FTIR, and SEM all indicate the presence of alumosilicate network structures in the hydration products, mainly N-A-S-H and C-A-S-H gels.

Long-time quantum scrambling and generalized tensor product structures

Long-time quantum scrambling and generalized tensor product structures

Special RCA based sensitive point‐of‐care detection of HPV mRNA for cervical cancer screening

AbstractDeveloping the sensitive point‐of‐care testing (POCT) of oncogenic nucleic acids from human papillomavirus (HPV) infection is essential in preventing cervical cancer, especially in resource‐limited settings. Rolling circle amplification (RCA) is attractive in achieving POCT via nucleic acid‐based aggregation under isothermal conditions. However, the influence of RCA product structure on the aggregation remains unexplored resulting in limited sensitivity. Here, a minimum secondary structured RCA technique (MSS‐RCA) is developed by designing a unique circular template, demonstrating significantly enhanced detection sensitivity with only one amplification step and one primer under isothermal conditions. The amplification efficiency of MSS‐RCA could be kinetically manipulated by controlling the secondary structure of the circular template. Introducing the invertase probe to MSS‐RCA, HPV16 E6/E7 nucleic acid target was detected with a personal glucose meter (PGM) with a sensitivity of 5 fm (50 zmol in 10 µL). This integrated MSS‐RCA‐PGM detection system was successfully applied to detect HPV16 E6/E7 mRNA extracted from 54 cervical swab samples reaching a positive predictive value of 100.00% and negative predictive values of 96.00% (77.77% to 99.40%, 95% CI). MSS‐RCA‐PGM provides a sensitive POCT platform for the detection of nucleic acid biomarkers for screening of cervical cancer or other diseases.

Thiadiazole/Thiadiazine Derivatives as Insecticidal Agent: Design, Synthesis, and Biological Assessment of 1,3,4-(Thiadiazine/Thiadiazole)-Benzenesulfonamide Derivatives as IGRs Analogues against Spodoptera littoralis.

In keeping with our investigation, a simple and practical synthesis of novel heterocyclic compounds with a sulfamoyl moiety that can be employed as insecticidal agents was reported. The compound 2-hydrazinyl-N-(4-sulfamoylphenyl)-2-thioxoacetamide 1 was coupled smoothly with triethylorthoformate or a variety of halo compounds, namely phenacyl chloride, chloroacetyl chloride, chloroacetaldehyde, chloroacetone, 1,3-dichloropropane, 1,2-dichloroethane, ethyl chloroformate, 2,3-dichloro-1,4-naphthoquinone, and chloroanil respectively, which afforded the 1,3,4-thiadiazole and 1,3,4-thiadiazine derivatives. The new products structure was determined using elemental and spectral analysis. Under laboratory conditions, the biological and toxicological effects of the synthetic compounds were also evaluated as insecticides against Spodoptera littoralis (Boisd.). Compounds 3 and 5 had LC50 values of 6.42 and 6.90 mg/L, respectively. The investigated compounds (from 2 to 11) had been undergoing molecular docking investigation for prediction of the optimal arrangement and strength of binding between the ligand (herein, the investigated compounds (from 2 to 11)) and a receptor (herein, the 2CH5) molecule. The binding affinity within docking score (S, kcal/mol) ranged between -8.23 (for compound 5), -8.12 (for compound 3) and -8.03 (for compound 9) to -6.01 (for compound 8). These compounds were shown to have a variety of binding interactions within the 2CH5 active site, as evidenced by protein-ligand docking configurations. This study gives evidence that those compounds have 2CH5-inhibitory capabilities and hence may be used for 2CH5-targeting development. Furthermore, the three top-ranked compounds (5, 3, and 9) and the standard buprofezin were subjected to density functional theory (DFT) analysis. The highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) energy difference (ΔE) of compounds 5, 3, and 9 was found to be comparable to that of buprofezin. These findings highlighted the potential and relevance of charge transfer at the molecular level.

A novel bio-adsorbent of CoFe2O4@SiO2 core-shell nanoparticles modified with persimmon tannin for simultaneous Au(III) ions adsorption and reduction

A novel bio-adsorbent was synthesized by the reaction between persimmon tannin (PT) and cobalt ferrite (CoFe2O4) with glutaraldehyde crosslinking, assigned as CoFe2O4@SiO2@PT. The product structure was confirmed by FTIR, XRD, TEM, DSC/TGA, and VSM. The results confirmed that the adsorbent had been successfully prepared and its surface had hydroxyl groups, which gave a great active site for Au(III) adsorption. As tested by batch system results, the kinetic data were consistent with the pseudo-second-order equation, while the adsorption equilibrium data fit well with the Langmuir model. The competitive adsorption test indicated that the adsorbent had a good preference to adsorb Au(III) over other coexisting ions. The Au(III) adsorption capacity of the adsorbent was 881.91 mg/g. It is greater than that of the reported adsorbents. The characterization by XRD, EDX, and SAED suggested that the adsorbed Au(III) was reduced to Au(0) particles as facilitated by the available functional groups. This adsorbent may be one of the good choices for the preconcentration and recovery of Au(III) from e-waste.

A synthesis of styrene-grafted starch accompanied with reaction condition optimization and microstructural and macroscopic property analysis

Styrene grafting is efficient to alter starch macroscopic property. Nevertheless, reaction mechanism, condition and products structure and properties are blurry. A deep exploration is necessary. Herein, K2S2O8 and styrene were chosen for corn starch modification. Reaction conditions involving K2S2O8 and styrene amounts, temperature and period were explored. Concurrently, microstructural and macroscopic properties of modified starches were explored via FT-IR, XPS, 13C NMR, GPC, XRD, SEM, TGA, DSC, CA and water dispersibility analysis. Main results reveal that K2S2O8 and styrene amounts, temperature and period as 3 and 200 wt%, 50 °C and 3 h is an optimized condition for starch grafting styrene, achieving a grafting yield (GY) as 45.8 wt%. GPC, XPS and 13C NMR analysis certified successful grafting and grafting mainly occurred at C-3 site OH within glucose unit. This variation converted starch crystalline shape transformation from A-typed to V-typed accompanied with crystallinity, thermal-stability and swelling characteristic decrease and surface hydrophobicity elevation. With GY increased from 0 to 45.8 wt% crystallinity decreased from 38.7 to 15.1%, thermal-decomposition temperature decreased by 10 °C, gelatinization temperature and CA increased by 50 °C and 70°, respectively. It seems a small amount styrene grafting can alter starch macroscopic property such as hydrophilicity efficiently, readily to manufacture hydrophobic starch. This hydrophobic starch might have a potential use in plastic industry, enlarging starch use application, meaningful.

Changes in the Glucose Concentration Affect the Formation of Humic-like Substances in Polyphenol-Maillard Reactions Involving Gibbsite.

The polyphenol-Maillard reaction is considered one of the important pathways in the formation of humic-like substances (HLSs). Glucose serves as a microbial energy source that drives the humification process. However, the effects of changes in glucose, particularly its concentration, on abiotic pathways remain unclear. Given that the polyphenol-Maillard reaction requires high precursor concentrations and elevated temperatures (which are not present in soil), gibbsite was used as a catalyst to overcome energetic barriers. Catechol and glycine were introduced in fixed concentrations into a phosphate-buffered solution containing gibbsite using the liquid shake-flask incubation method, while the concentration of glucose was controlled in a sterile incubation system. The supernatant fluid and HLS components were dynamically extracted over a period of 360 h for analysis, thus revealing the influence of different glucose concentrations on abiotic humification pathways. The results showed the following: (1) The addition of glucose led to a higher degree of aromatic condensation in the supernatant fluid. In contrast, the supernatant fluid without glucose (Glu0) and the control group without any Maillard precursor (CK control group) exhibited lower degrees of aromatic condensation. Although the total organic C (TOC) content in the supernatant fluid decreased in all treatments during the incubation period, the addition of Maillard precursors effectively mitigated the decreasing trend of TOC content. (2) While the C content of humic-like acid (CHLA) and the CHLA/CFLA ratio (the ratio of humic-like acid to fulvic-like acid) showed varying increases after incubation, the addition of Maillard precursors resulted in a more noticeable increase in CHLA content and the CHLA/CFLA ratio compared to the CK control group. This indicated that more FLA was converted into HLA, which exhibited a higher degree of condensation and humification, thus improving the quality of HLS. The addition of glycine and catechol without glucose or with a glucose concentration of 0.06 mol/L was particularly beneficial in enhancing the degree of HLA humification. Furthermore, the presence of glycine and catechol, as well as higher concentrations of glucose, promoted the production of N-containing compounds in HLA. (3) The presence of Maillard precursors enhanced the stretching vibration of the hydroxyl group (-OH) of HLA. After the polyphenol-Maillard reaction of glycine and catechol with glucose concentrations of 0, 0.03, 0.06, 0.12, or 0.24 mol/L, the aromatic C structure in HLA products increased, while the carboxyl group decreased. The presence of Maillard precursors facilitated the accumulation of polysaccharides in HLA with higher glucose concentrations, ultimately promoting the formation of Al-O bonds. However, the quantities of phenolic groups and phenols in HLA decreased to varying extents.

Validated chromatographic methods for determination of teriflunomide and investigation of its intrinsic stability

Two rapid, precise, and sensitive stability-indicating high performance chromatographic methods for the measurement of Teriflunomide in its degradation products’ existence were developed. These were RP-HPLC and HPTLC using UV detector. HPLC separation was accomplished utilizing Thermo BDS hypercil C18 column (250 × 4.6 mm, 5 μm) and acetonitrile: 0.03 M potassium dihydrogen phosphate: triethylamine (50:50:0.1%, by volume) as mobile phase at flow rate of 1mL/min. The separated peaks were detected at 250.0 nm. The densitometric approach was conducted utilizing HPTLC 60 F254 silica gel plates, and a developing system of benzene: ethanol: acetic acid (7.5:1:0.25, by volume) and detection was done at 250.0 nm. The developed approaches were evaluated regarding the International Conference on Harmonization (ICH) instructions. The calibration curves of both techniques were constructed with linearity ranges of (5-100) µg/mL and (2–10) µg /band, for HPLC and densitometric determination, consecutively. Teriflunomide was exposed to base and acid hydrolysis, oxidation using H2O2 and finally, thermal degradation as stated in ICH guidelines. The degradation product structures’ elucidation was achieved through LC-MS.