Complex Products Research Articles

Total Synthesis of Ryanodane Diterpenoids Garajonone and 3‐epi‐Garajonone

AbstractRyanodane diterpenes are structurally complex natural products that are well‐known for their high degree of oxidation and the challenges associated with synthesizing them within the terpene class. Herein, we present a two‐stage synthetic strategy that draws inspiration from the broad biosynthesis of terpenes, allowing us to achieve the first chemical synthesis of garajonone, a ryanodane diterpenoid that occurs naturally at low abundance, as well as its epimer, 3‐epi‐garajonone. The key to this success lies in the rapid construction of the carbon framework of the target molecule by employing an early‐stage palladium‐catalyzed Heck/carbonylative esterification cascade annulation, followed by successive late‐stage selective redox manipulation to establish the desired oxidation state of the molecule. This research not only showcases the synthesis of garajonone and its epimer but also provides a platform for the chemical synthesis of other members and analogs of this complex diterpenoid family.

Total Synthesis of Ryanodane Diterpenoids Garajonone and 3-epi-Garajonone.

Ryanodane diterpenes are structurally complex natural products that are well-known for their high degree of oxidation and the challenges associated with synthesizing them within the terpene class. Herein, we present a two-stage synthetic strategy that draws inspiration from the broad biosynthesis of terpenes, allowing us to achieve the first chemical synthesis of garajonone, a ryanodane diterpenoid that occurs naturally at low abundance, as well as its epimer, 3-epi-garajonone. The key to this success lies in the rapid construction of the carbon framework of the target molecule by employing an early-stage palladium-catalyzed Heck/carbonylative esterification cascade annulation, followed by successive late-stage selective redox manipulation to establish the desired oxidation state of the molecule. This research not only showcases the synthesis of garajonone and its epimer but also provides a platform for the chemical synthesis of other members and analogs of this complex diterpenoid family.

Orderly Coating of Bilayer Polymer to Tailor Microenvironment for Efficient C−N Coupling Toward Highly Selective Urea Electrosynthesis

AbstractElectrosynthesis of urea from co‐reduction of carbon dioxide and nitrate is a promising alternative to the industrial process. However, the overwhelming existence of proton and nitrate as well as the insufficient supply of CO2 at the reaction interface usually result in complex product distributions from individual nitrate reduction or hydrogen evolution, instead of C−N coupling. In this work, we systematically optimize this microenvironment through orderly coating of bilayer polymer to specifically tackle the above challenges. Polymer of intrinsic microporosity is chosen as the upper polymer to achieve physical sieving, realizing low water diffusivity for suppressing hydrogen evolution and high gas permeability for smooth mass transfer of CO2 at the same time. Polyaniline with abundant basic amino groups is capable of triggering chemical interaction with acidic CO2 molecules, so that is used as the underlying polymer to serve as CO2 concentrator and facilitate the carbon source supply for C−N coupling. Within this tailored microenvironment, a maximum urea generation yield rate of 1671.6 μg h−1 mg−1 and a high Faradaic efficiency of 75.3 % are delivered once coupled with efficient electrocatalyst with neighboring active sites, which is among the most efficient system of urea electrosynthesis.

Experimental and advanced equilibrium studies on the enhanced adsorption of phosphate, cadmium, and safranin dye pollutants using methoxy exfoliated glauconite.

Natural glauconite, as a mixed-layered clay mineral, was subjected to exfoliation processes, producing silicate monolayers or individual sheets that were further modified with methanol into methoxy exfoliated glauconite (Mth/EXG). The structure was assessed as an enhanced adsorbent for three types of common water contaminants, including phosphate (PO4 3-), safranin-O dye (SFR), and cadmium metal ions (Cd2+). The Mth/EXG structure achieved promising adsorption capacities at the saturation points equal to 269.9mg/g for PO4 3-, 312mg/g for SFR, and 234.5mg/g for Cd2+ which are significantly better than the reported values for several studied adsorbents of higher costs and complex production procedures. The adsorption processes and the predicted regulated mechanisms in terms of the adsorbate/adsorbent interface were illustrated based on the steric and energetic findings that correspond to the applied monolayer equilibrium model of one energy site. The structure displays active site densities of 82.5mg/g (PO4 3-), 136.3mg/g (SFR), and 83.4mg/g (Cd2+), which illustrate the high uptake performance of SFR. Also, the steric parameters reflected the suitability of each existing site to be filled with 4 ions of PO4 3-, SFR, and Cd2+. The adsorption energy (less than 40kJ/mol) in conjunction with free adsorption energy from D-R model (8-16kJ/mol) and steric parameters validate the dominant impact of the multi-ionic physical mechanisms (hydrogen bonding and van der Waals forces), in addition to the assistant impact of some weak chemical processes that might be assigned to the formed inner-sphere complex. Also, these reactions all occurred spontaneously with exothermic behaviors according to the thermodynamic functions. Additionally, the structure exhibit significant affinity for the studied pollutants even in the existing of completive chemical including anions, cations and organic molecules.

Wooden hafting technology in the early Neanderthal site of Poggetti Vecchi (Italy)

The invention of hafted tools, between about 500 Ka and 250 Ka years ago, was a fundamental technological innovation that has shaped human social, cognitive, and biological capabilities. Despite the recurrent evidence of hafting observed on lithic tools, handles from this period are rare since they were probably made of perishable materials. Three exceptional wooden sticks interpreted as handles have been found in the Poggetti Vecchi site, allowing a deeper investigation of the technical capabilities of the early Neanderthals who frequented the site around 170,000 years ago. The handles and the lithic tools with hafting traces were analysed using a techno-functional approach, suggesting that they could have been attached to each other to create a specific composite hafted tool. The efficiency of the composite hafted tool was tested through a detailed experimental programme. The results highlighted, for the first time, the complex production processes used to create a composite hafted tool that could have been used to butcher the carcases of the large fauna that are well attested at the site.

Electrochemical Synthesis of Metal Complexes Using Dissolving Anodes.

The use of dissolving metal electrodes for the direct electrochemical synthesis of metal complexes has been used widely in the last decade. A major benefit of the electrochemical approach is the minimal by-products resulting from the synthesis. As such, metal complexes can be produced on-demand and used directly in catalysis without the need for purification. Furthermore, the electrochemical method enables the production of metal complexes that cannot be synthesized using other methods, including those with base-sensitive ligands. General principles of the electrochemical method and recent advances in the field are discussed.

Rapid and Specific Detection of Bacillus cereus Using Phage Protein-Based Lateral Flow Assays.

Rapid and precise diagnostic techniques are essential for identifying foodborne pathogens, including Bacillus cereus (B. cereus), which poses significant challenges to food safety. Traditional detection methods are limited by long incubation times and high costs. In this context, gold nanoparticle (AuNP)-based lateral flow assays (LFAs) are emerging as valuable tools for rapid screening. However, the use of antibodies in LFAs faces challenges, including complex production processes, ethical concerns, or variability. Here, we address these challenges by proposing an innovative approach using bacteriophage-derived proteins for pathogen detection on LFAs. We used the engineered endolysin cell-wall-binding domain (CBD) and distal tail proteins (Dit) from bacteriophages that specifically target B. cereus. The protein-binding properties, essential for the formation of efficient capture and detection biointerfaces in LFAs, were extensively characterized from the microstructural to the LFA device level. Machine-learning models leverage knowledge of the protein sequence to predict advantageous protein orientations on the nitrocellulose membrane and AuNPs. The study of the biointerface binding quantified the degree of attachment of AuNPs to bacteria, providing, for the first time, a microscopic model of the number of AuNPs binding to bacteria. It highlighted the binding of up to one hundred 40 nm AuNPs per bacterium in conditions mimicking LFAs. Eventually, phage proteins were demonstrated as efficient bioreceptors in a straightforward LFA prototype combining the two proteins, providing a rapid colorimetric response within 15 min upon the detection of 105 B. cereus cells. Recombinantly produced phage binding proteins present an opportunity to generate a customizable library of proteins with precise binding capabilities, offering a cost-effective and ethical alternative to antibodies. This study enhances our understanding of phage protein biointerfaces, laying the groundwork for their utilization as efficient bioreceptors in LFAs and rapid point-of-care diagnostic assays, thus potentially strengthening public health measures.

Enantioselective Synthesis of Azatricycles via Post-Ugi Cyclizations.

We report a new method to create enantioenriched azatricycles using chiral α-amino acids in a two-step process after an Ugi reaction. Amino acids are great building blocks for making pure chiral molecules. Using chiral natural molecules in multicomponent reactions (MCRs) helps increase their variety by adding new chiral centers. The Ugi reaction, discovered by Ivar Karl Ugi in 1959, is a versatile MCR that helps create complex molecular structures and natural products through additional transformations called post-Ugi modifications. Designing these modifications requires selecting the right amine, acid, aldehyde/ketone, and isocyanide. Amino acids, with their primary amine and carboxylic acid groups and a pre-existing chiral center, are ideal for making diverse and selective post-Ugi modifications. Our method uses ipso-cyclization and aza-Michael cyclization with hypervalent iodine to create various azaspirotricyclic structures with high stereocontrol. This approach works well with different substrates and shows promise for further development in drug discovery.

Robot arm grasping based on YOLOv5 in the perspective of automated production

Abstract The rapid development of industrial intelligence has gradually expanded the application of automated production. As a typical automated production equipment, the robotic arm still faces the problems of low grasping efficiency and high control costs when facing highly integrated and miniaturized components. Given this, to improve the grasping level of the robotic arm in complex production environments, this study first constructs a kinematic mathematical model of the robotic arm. Secondly, based on the algorithm that You Only Look Once, improvements are made to its convolution operation and feature extraction modules, ultimately proposing a new type of robotic arm grasping control model. The results showed that the loss test value of the new model was the lowest at 2.75, the average detection error of the captured object was the lowest at 0.003, and the average detection time was the shortest at 1.28 seconds. The highest success rate for grasping six types of industrial parts was 94%, and the lowest average energy consumption was 35.67 joules. Therefore, research models can significantly improve the grasping performance of robotic arms under various complex conditions, thereby achieving efficient manipulation of robotic arms in industrial automation.

Low-energy (0–9 eV) electron interaction with gas phase 1,3-dichlorobenzene: an experimental and theoretical study

Abstract Dichlorobenzene used widely in industry for the synthesis of complex products, such as polymers. The processes using this compound require, as the initial step, the breakage of the C–Cl bond. In this work, we study the interaction of electrons with 1,3 dichlorobenzene molecules not only below 2 eV [M Mahmoodi-Darian et al 2001 J. Phys. Chem. A 113 11923–14929] but also at higher energies, i.e., up to 10 eV. In this investigated energy range, the electron induces the cleavage of the C–Cl bond producing essentially a Cl− anion and the chlorobenzene radical via dissociative electron attachment. The experimental measurements are completed with quantum scattering treatments providing the resonant states and also the integral scattering cross sections. These outcomes may potentially contribute to elaborate synthesis strategies using electrons (i.e., cold plasma, surface plasmon resonance, …).

Cell-Free Screening, Production and Animal Testing of a STI-Related Chlamydial Major Outer Membrane Protein Supported in Nanolipoproteins.

Vaccine development against Chlamydia, a prevalent sexually transmitted infection (STI), is imperative due to its global public health impact. However, significant challenges arise in the production of effective subunit vaccines based on recombinant protein antigens, particularly with membrane proteins like the Major Outer Membrane Protein (MOMP). Cell-free protein synthesis (CFPS) technology is an attractive approach to address these challenges as a method of high-throughput membrane protein and protein complex production coupled with nanolipoprotein particles (NLPs). NLPs provide a supporting scaffold while allowing easy adjuvant addition during formulation. Over the last decade, we have been working toward the production and characterization of MOMP-NLP complexes for vaccine testing. The work presented here highlights the expression and biophysical analyses, including transmission electron microscopy (TEM) and dynamic light scattering (DLS), which confirm the formation and functionality of MOMP-NLP complexes for use in animal studies. Moreover, immunization studies in preclinical models compare the past and present protective efficacy of MOMP-NLP formulations, particularly when co-adjuvanted with CpG and FSL1. Ex vivo assessments further highlight the immunomodulatory effects of MOMP-NLP vaccinations, emphasizing their potential to elicit robust immune responses. However, further research is warranted to optimize vaccine formulations further, validate efficacy against Chlamydia trachomatis, and better understand the underlying mechanisms of immune response.

The structure and dynamics of the auto parts industry: Product space and complexity perspectives

Economic structures are strong determinants of diversification, growth, innovation, inequality, and many other socio-economic outcomes; however, structural change's effect on specific industries remains unexplored. This study investigates Japan's automotive components industry, analyzing its productive structure (the auto parts product space) and structural change process. We develop exploratory and econometric analyses that unify the measures of product relatedness and complexity. The firm-level data analysis shows that specific structural properties in international and domestic economies also exist in the automobile industry. This fractal structure implies that common principles and regularities underlie the formation of productive structures, notwithstanding the economies’ size, maturity, and industrial scope differences. The exploratory and econometric analyses indicate that the events of a product's appearance are not random but are significantly contingent on the network topology of the product space. Furthermore, network topology significantly impacts the development of complex products with sophisticated capabilities.

Overcoming Product Catalog Challenges in Telecom : A Technical Perspective

This comprehensive article explores the intricate challenges telecom providers face in managing complex product catalogs across multiple customer touchpoints. With the global telecom market projected to reach $2.47 trillion by 2028, efficient catalog management is crucial for maintaining competitiveness and customer satisfaction. The article delves into the multifaceted complexities of telecom product catalogs, including regional pricing variations, dynamic promotional offers, and the need for real-time synchronization across platforms. It outlines key challenges such as catalog complexity, slow data retrieval, frequent updates, third-party integration latencies, high traffic spikes, and campaign management inconsistencies. The article then presents innovative technical solutions and best practices, including the adoption of industry-leading catalog solutions, leveraging ElasticSearch for faster data retrieval, implementing differential processing for updates, preprocessing third-party integrations, utilizing dynamic UI templates, employing advanced campaign management tools, and implementing inventory prefetching. These solutions aim to enhance operational efficiency, improve customer experiences, and accelerate time-to-market in the rapidly evolving telecom industry.

Solid-liquid phase microextractive adsorption of bio-lactic acid by a novel microextractor immobilizing ionic liquid A336

The separation of biochemicals poses significant challenges, such as complex product composition, strong hydrophilicity, and high boiling point, which leads to laborious procedures, low yield, and high energy consumption. These obstacles have become bottlenecks for the industrialization of biochemicals. To enhance the efficient separation of bio-lactic acid, a novel microextractor, PS-A336, was synthesized through the copolymerization of ionic liquid (IL) A336 onto a polystyrene (PS) skeleton and further employed to investigate the solid–liquid phase microextractive adsorption (SLPMA). Extensive analysis of PS-A336 microstructure and chemical composition demonstrated its exceptional performance with a rapid (< 20 min) adsorption capacity (1150 mg/g) for LA in the batch system, which is the highest value reported and 11.0 times higher than that of the pristine supports. PS-A336 maintained its stability even after 15 cycles of column chromatography. Its adsorption behavior also fits the common thermodynamic and kinetic models, and it is better for the SLPMA kinetic model established on Fick diffusion law. Additionally, PS-A336 exhibited high adsorption capacity and selectivity for LA from the fermentation broth, achieving above 98 % removal ratios to proteins, inorganic salts, and pigments. The double hydrogen bonds between PS-A336 and LA were identified as the primary driving forces for SLPMA following theoretical and structural investigations. Notably, the immobilized IL in PS-A336 exhibited a remarkable microextraction effect, i.e., an increase in extractive capacity at least 16.6 times due to 59.8-fold improvement in the interface area compared with the bulk IL, which is 28.6 times higher than the adsorption capacity of PS skeleton. Our findings provided new insights into the combination of extraction and adsorption, as well as valuable guidance for the efficient separation of bio-based chemicals.

Bone and antler products from the Toretskoye urban settlement of the 15th century ad

Products made of bone and antler complement the characteristics of the material culture of the Toretskoye urban settlement, a major centre of crafts and international trade in the Kazan Khanate. In accordance with the general dating of the single-layer site, all items made of bone and antler have a reliable period of existence within the 15th century AD. Based on frequent numismatic material and other related context, the products receive the status of a chronological and, in some cases, ethnocultural reference point, and in terms of inventory and manufacturing techniques they represent products of urban production. No specialized bone-carving workshops have been found at the site; however, the presence of blanks and faulty products in the coppersmith and blacksmith workshops makes it possible to conclude that bone and antler processing was a related craft of complex production.

Labneh: A Retail Market Analysis and Selected Product Characterization.

Labneh is a popular fermented dairy product, which contemporarily has diversified into a varied range of styles, formulated with the inclusion of multiple additives, and is sourced across the globe. This has driven labneh's emergence as a complex product with varying textural and rheological characteristics. The lack of scientific literature about labneh products available in the United Arab Emirates (UAE) market and their characterization has prompted this study. A detailed UAE market analysis of labneh for label, formulation, nutrition, and price variability was conducted. Surveyed labneh products were categorized as unpackaged, multinational company (MNC), small and medium enterprise (SME), and specialty products. They differed in manufacturing, such as acid ± enzyme coagulation with/without post-fermentation heat treatment, and contained various stabilizers, emulsifiers, preservatives, and processing aids. Interestingly, almost equal proportions, 64.7% and 67%, of MNC and SME labneh contained additives, respectively. All MNC labneh were post-heat-treated, in contrast to only 7% of SME labneh. Organic labneh and non-bovine milk-based labneh are not yet widely available. The second part of the study involved the physicochemical characterization of a select number of packaged labneh that were categorized in accordance with fat content as high-fat (17-18%), full-fat (7.1-8%), and lite-fat (3.5-4.5%). High-fat labneh showed a significantly higher complex viscosity, complex modulus, hardness, adhesiveness, stringiness, and fracturability, followed by lite-fat labneh compared to full-fat labneh, especially when it contained pectin. Full-fat labneh with added gums (and starch) and high-fat labneh with gums showed a significantly lower complex modulus compared to their respective control labneh. This study highlights the variety of commercial labneh products available and differences in their formulation, manufacturing, and composition, and provides specific dependencies of materials with their physicochemical characteristics.

Generation of Triplet States by Host‐Stabilized Through‐Space Conjugation for the Construction of Efficient Supramolecular Photocatalysts

AbstractPromoting the generation of triplet states is essential for developing efficient photocatalytic systems. This research presents a novel approach of host‐stabilized through‐space conjugation via the combination of covalent and non‐covalent methods. The designed building block, 4,4′‐(1,4(1,4)‐dibenzene cyclohexaphane‐1,4‐diyl)bis(1‐phenylpyridinium) chloride, features inherently stable through‐space conjugation. When this block forms a 1 : 1 host–guest complex with cucurbit[8]uril, the through‐space conjugation is further stabilized within the confined cavity. Both the generation and lifetime of triplet state are significantly increased, resulting from the host‐stabilized through‐space conjugation. Additionally, the ultrahigh binding constant of 6.58×1014 M−1 ensures the persistence of host‐stabilization effect. As a result, the host–guest complex acts as a highly efficient catalyst in the photocatalytic oxidation of thioether and aromatic alcohol. In the photodegradation of lignin, a complex natural product, the host–guest complex also exhibits high efficiency, demonstrating its robustness. This line of research is anticipated to enrich the toolbox of supramolecular photochemistry and provide a strategy for fabricating efficient supramolecular photocatalysts.

Influence of Density of 3D Printing Using the Fdm Method on Productivity and Mechanical Properties of ABS

The economic and technical advantages of 3D printing make it a possible replacement for conventional production processes, especially for complex products and small batches. It is important to point out that technological parameters of 3D printing, such as layer thickness, print density, print speed, melting temperature, and table temperature, have a significant impact on the mechanical properties and productivity of parts obtained by 3D printing. Because of all the above, there is a great interest in research in this area. The paper presents the results of testing the tensile strength of the ABS polymer, in which two parameters were varied: the thickness of the print layer (0.39 mm) and the print density of 60–100% in steps of 10% each. The samples were obtained on a ZORTRAX M200+ 3D printer using fused filament deposition (FDM) technology. The selected thickness of the printing layer is relatively large, and with it, parts with lower accuracy and high surface roughness are obtained, although at the same time high productivity is achieved, which can satisfy some requirements. The obtained tensile strength values show that increasing the print density leads to an increase in its value, with a deviation in the sample with a print density of 100%, whereas the tensile strength values are comparable to the values obtained by other authors.

The Relationship Between Production Efficiency and Factor Allocation Efficiency: A Case Study Based on Thermal Power in China

This paper introduces a novel decomposition method for analyzing production efficiency based on the Data Envelopment Analysis framework, addressing the limitations of traditional approaches that often fail to isolate the contributions of individual factors. The proposed method disaggregates production efficiency into capacity utilization, labor utilization efficiency, energy utilization efficiency, and technological change, providing a more granular view of how different factors contribute to overall efficiency. By incorporating both contemporaneous and intertemporal perspectives, this approach enables a comprehensive understanding of efficiency dynamics and factor interactions over time. To demonstrate the feasibility and robustness of the proposed method, we apply it to the thermal power industry using data from 30 Chinese provinces covering the period from 2011 to 2021. The empirical results validate the effectiveness of the decomposition framework, revealing distinct regional disparities in efficiency and providing insights for targeted resource optimization strategies. Based on these findings, we offer recommendations to enhance capacity utilization, improve energy efficiency, and support sustainable development within the thermal power sector. This research contributes a powerful analytical tool for disaggregating production efficiency and offers a theoretical foundation for future studies seeking to understand the nuanced relationships between comprehensive production efficiency and single-factor efficiencies, thereby supporting better policy and management decisions in complex production systems.

Sustainability assessment of additive manufacturing end-of-life material management

Additive manufacturing (AM) methods enable complex, customized, and on-demand production of many products from different material types across various industries. The growing demand for flexible and more sustainable manufacturing solutions places AM in the mix of processes considered for non-commodities. However, AM processes also present unintentional environmental releases in end-of-life (EoL) material management, compromising overall sustainability. Data availability to assess the sustainability of individual EoL material management from individual AM processes is limited. Even so, EoL materials generated across AM practices frequently overlap, supporting high-level assessment as an alternative approach. Therefore, a holistic AM EoL material management sustainability analysis was completed using a customized list of efficiency, environmental, energy, and economic indicators from the Gauging Reaction Effectiveness for the Environmental Sustainability of Chemistries with a multi-Objective Process Evaluator (GREENSCOPE) methodology. Subsequently, this assessment identified low material recycling rates and high energy costs in some EoL material management processes, such as incineration and recovery. Subsequently, a trade-off analysis was performed to determine process modification opportunities, including implementing recycling to reduce the amount of hazardous waste at the expense of additional energy and cost investment. The AM EoL-specific sustainability analysis serves as a resource to offer insights and empower policymakers and stakeholders to enhance pollution prevention strategies and optimize the existing EoL material management processes.