Journal of the American Chemical Society

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTPreparation of Graphitic OxideWilliam S. Hummers Jr. and Richard E. OffemanCite this: J. Am. Chem. Soc. 1958, 80, 6, 1339Publication Date (Print):March 1, 1958Publication History Published online1 May 2002Published inissue 1 March 1958https://pubs.acs.org/doi/10.1021/ja01539a017https://doi.org/10.1021/ja01539a017research-articleACS PublicationsRequest reuse permissionsArticle Views106696Altmetric-Citations26571LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAdsorption of Gases in Multimolecular LayersStephen Brunauer, P. H. Emmett, and Edward TellerCite this: J. Am. Chem. Soc. 1938, 60, 2, 309–319Publication Date (Print):February 1, 1938Publication History Published online1 May 2002Published inissue 1 February 1938https://pubs.acs.org/doi/10.1021/ja01269a023https://doi.org/10.1021/ja01269a023research-articleACS PublicationsRequest reuse permissionsArticle Views46810Altmetric-Citations21813LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTTHE ADSORPTION OF GASES ON PLANE SURFACES OF GLASS, MICA AND PLATINUM.Irving LangmuirCite this: J. Am. Chem. Soc. 1918, 40, 9, 1361–1403Publication Date (Print):September 1, 1918Publication History Published online1 May 2002Published inissue 1 September 1918https://pubs.acs.org/doi/10.1021/ja02242a004https://doi.org/10.1021/ja02242a004research-articleACS PublicationsRequest reuse permissionsArticle Views24474Altmetric-Citations17033LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

Two organolead halide perovskite nanocrystals, CH(3)NH(3)PbBr(3) and CH(3)NH(3)PbI(3), were found to efficiently sensitize TiO(2) for visible-light conversion in photoelectrochemical cells. When self-assembled on mesoporous TiO(2) films, the nanocrystalline perovskites exhibit strong band-gap absorptions as semiconductors. The CH(3)NH(3)PbI(3)-based photocell with spectral sensitivity of up to 800 nm yielded a solar energy conversion efficiency of 3.8%. The CH(3)NH(3)PbBr(3)-based cell showed a high photovoltage of 0.96 V with an external quantum conversion efficiency of 65%.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTPrinciples of Polymer Chemistry.Maurice L. HugginsCite this: J. Am. Chem. Soc. 1954, 76, 10, 2854Publication Date (Print):May 1, 1954Publication History Published online1 May 2002Published inissue 1 May 1954https://pubs.acs.org/doi/10.1021/ja01639a090https://doi.org/10.1021/ja01639a090research-articleACS PublicationsRequest reuse permissionsArticle Views917Altmetric-Citations20LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

The parametrization and testing of the OPLS all-atom force field for organic molecules and peptides are described. Parameters for both torsional and nonbonded energetics have been derived, while the bond stretching and angle bending parameters have been adopted mostly from the AMBER all-atom force field. The torsional parameters were determined by fitting to rotational energy profiles obtained from ab initio molecular orbital calculations at the RHF/6-31G*//RHF/6-31G* level for more than 50 organic molecules and ions. The quality of the fits was high with average errors for conformational energies of less than 0.2 kcal/mol. The force-field results for molecular structures are also demonstrated to closely match the ab initio predictions. The nonbonded parameters were developed in conjunction with Monte Carlo statistical mechanics simulations by computing thermodynamic and structural properties for 34 pure organic liquids including alkanes, alkenes, alcohols, ethers, acetals, thiols, sulfides, disulfides, aldehydes, ketones, and amides. Average errors in comparison with experimental data are 2% for heats of vaporization and densities. The Monte Carlo simulations included sampling all internal and intermolecular degrees of freedom. It is found that such non-polar and monofunctional systems do not show significant condensed-phase effects on internal energies in going from the gas phase to the pure liquids.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTThe Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen IsothermsElliott P. Barrett, Leslie G. Joyner, and Paul P. HalendaCite this: J. Am. Chem. Soc. 1951, 73, 1, 373–380Publication Date (Print):January 1, 1951Publication History Published online1 May 2002Published inissue 1 January 1951https://pubs.acs.org/doi/10.1021/ja01145a126https://doi.org/10.1021/ja01145a126research-articleACS PublicationsRequest reuse permissionsArticle Views22005Altmetric-Citations10643LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

Abstract: We present the derivation of a new molecular mechanical force field for simulating the structures, conformational energies, and interaction energies of proteins, nucleic acids, and many related organic molecules in condensed phases. This effective two-body force field is the successor to the Weiner et al. force field and was developed with some of the same philosophies, such as the use of a simple diagonal potential function and electrostatic potential fit atom centered charges. The need for a 10-12 function for representing hydrogen bonds is no longer necessary due to the improved performance of the new charge model and new van der Waals parameters. These new charges are determined using a 6-31G * basis set and restrained electrostatic potential (RESP) fitting and have been shown to reproduce interaction energies, free energies of solvation, and conformational energies of simple small molecules to a good degree of accuracy. Furthermore, the new RESP charges exhibit less variability as a function of the molecular conformation used in the charge determination. The new van der Waals parameters have been derived from liquid simulations and include hydrogen parameters which take into account the effects of any geminal electronegative atoms. The bonded parameters developed by Weiner et al. were modified as necessary to reproduce experimental vibrational frequencies and structures. Most of the simple dihedral parameters have been retained from Weiner et al., but a complex set of 4 and yj parameters which do a good job of reproducing the energies of the low-energy conformations of glycyl and alanyl dipeptides has been developed for the peptide backbone.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTDevelopment and use of quantum mechanical molecular models. 76. AM1: a new general purpose quantum mechanical molecular modelMichael J. S. Dewar, Eve G. Zoebisch, Eamonn F. Healy, and James J. P. StewartCite this: J. Am. Chem. Soc. 1985, 107, 13, 3902–3909Publication Date (Print):June 1, 1985Publication History Published online1 May 2002Published inissue 1 June 1985https://pubs.acs.org/doi/10.1021/ja00299a024https://doi.org/10.1021/ja00299a024research-articleACS PublicationsRequest reuse permissionsArticle Views9784Altmetric-Citations12058LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTThe Determination of Enzyme Dissociation ConstantsHans Lineweaver and Dean BurkCite this: J. Am. Chem. Soc. 1934, 56, 3, 658–666Publication Date (Print):March 1, 1934Publication History Published online1 May 2002Published inissue 1 March 1934https://doi.org/10.1021/ja01318a036RIGHTS & PERMISSIONSArticle Views17226Altmetric-Citations9769LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (854 KB) Get e-Alertsclose Get e-Alerts

Abstract The selective functionalization of methane under ambient conditions is widely regarded as a holy grail in chemistry, yet remains fundamentally limited not only by the inertness of the C–H bond but also by the transient nature of highly reactive intermediates. Short-lived species are often difficult to preserve and utilize prior to productive coupling, constraining accessible reaction pathways and product selectivity. Here, we establish a reaction framework based on in situ interfacial interception of reactive radicals, enabling the temporal coordination between radical lifetime and subsequent reaction processes. Plasma generates short-lived methyl radicals in immediate proximity to a gas–electrode interface, allowing their direct delivery and capture at the catalytic surface, while the electrochemical interface independently converts ammonia into surface-bound amino intermediates. Their coupling enables selective C–N bond formation. This spatially and temporally coordinated process allows highly reactive radical species to be synchronized with interfacial reaction steps, facilitating their productive utilization. Guided by density functional theory, we identify a nickel–cobalt layered double hydroxide catalyst that promotes interfacial coupling between *CH3 and *NH2 intermediates. The optimized system achieves a Faradaic efficiency of 54% for methylamine at 10 mA cm–2, with a productivity of 201 μmol cm–2 h–1 under ambient conditions. Beyond methane amination, this work demonstrates that coordinating the lifetime and transformation of reactive intermediates provides a generalizable strategy for catalytic control, offering new opportunities for the activation and selective transformation of inert molecules.

Abstract Primary amines are indispensable building blocks in pharmaceuticals, agrochemicals, and functional materials, yet their direct, modular synthesis from ammonia remains challenging. Here we report a carbonyl catalysis strategy that enables the direct synthesis of structurally complex primary amines from ammonia by integrating the conventional multistep sequence of protection, N–H functionalization, and deprotection into a single catalytic cycle. As a proof of concept, amino-trifluoromethylation of alkenes using ammonium salts and Togni reagent afforded a wide range of β-trifluoromethylated primary amines, including derivatives of complex natural products. 1,8-Diazafluorenone was uniquely competent as a carbonyl catalyst, highlighting the critical role of catalyst design in ammonia transformation. Mechanistic studies suggest that its distinctive electronic structure facilitates the formation of the N–H ketimine intermediate, a prerequisite for catalytic turnover. These findings establish carbonyl catalysis as a platform for the direct transformation of ammonia and demonstrate how protecting groups can function as catalysts.

Abstract Despite a surge of progress in both strategic approaches and reagent design, carbon insertion into indoles remains limited to electron-rich substrates, notwithstanding the prevalence of electron-poor (aza)indoles in medicinal chemistry. We report herein a radical-polar crossover strategy that overcomes this limitation through a photocatalytic, iodomethyl-radical-mediated cyclopropanation/autoxidation approach. The method enables access to a range of highly substituted, electron-poor quinolines, naphthyridines, and triazanaphthalenes, many of which are challenging to prepare by traditional syntheses. We demonstrate the modification of medicinally relevant (aza)indoles, and preliminary mechanistic observations support autoxidation via an anionic cyclopropane ring opening pathway.

Abstract Controlling the delivery of chemotherapy to the tumor site is a long-standing goal of the medical field, as it could not only enhance the anticancer activity of the treatment but also reduce damage to the rest of the body. The emergence of bioorthogonal catalysis as a strategy capable of mediating continuous drug production in a nonenzymatic fashion has created the opportunity to develop so-called “bioorthogonal therapies,” which aim to generate the anticancer agents inside the tumors. Herein, we describe a novel class of supramolecular materials comprising ultrathin palladium nanosheets and fluorenylmethoxycarbonyl-diphenylalanine that self-assemble in water to form injectable, self-healing, biocompatible catalytic gels that convert inactive prodyes and prodrugs into active small molecules. The relatively weak physicochemical cross-links generated by the hybrid metal-peptide fibers facilitate the flow of the gel under mild shear stress (shear-thinning), thereby enabling precise intratumoral injections in vivo and localized prodrug activation. The strategy was validated in an aggressive pancreatic cancer xenograft model in mice, setting out a new direction for the field of bioorthogonal therapies.

Abstract N-ethylamines are important motifs in pharmaceuticals and fine chemicals, but their selective synthesis from nitriles requires control over both nitrile reduction and amine availability at the catalyst-electrolyte interface. Herein, we investigate mixed Cu–Ni oxides for the aqueous electrocatalytic C–N coupling of acetonitrile (MeCN) with benzylamine (BA). The optimized Cu-NiO-0.5 catalyst affords N-ethylbenzylamine (EBA) in 75% yield with 87% selectivity and a mass-normalized formation rate of 12.5 mmol h–1 gcat–1 at −0.5 VRHE. Electrochemical testing indicates that the presence of CuO can promote the MeCN electrochemical reduction, generating abundant ethylimine for subsequent coupling. Meanwhile, the incorporation of Ni significantly enhances the adsorption of BA, accelerating the C–N coupling between the ethylimine and BA. In situ experimental measurements further confirm the sequential reduction-condensation-reduction pathway. Moreover, this strategy has also been proven to enable efficient C–N coupling between MeCN and various amine derivatives, giving the corresponding N-ethylated products in 58.3–84.6% yield and greater than 74% selectivity. This work offers an environmentally friendly strategy for the electrocatalytic synthesis of N-ethylamines.

Abstract The development in the synthesis of covalent organic frameworks (COFs) has been oriented toward the integration of simplicity, accessibility, stability, diversity, and functionality. However, a central bottleneck remains the lack of effective strategies for assembling simple, unsymmetric, and readily available molecules into highly ordered frameworks. Here, we report a practical synthesis of robust, diversified, and functional COFs via one-pot assembly from a low-cost and simple-structured molecule, 4-methyl-3-nitrobenzonitrile (MNBN). Leveraging the versatile but orthogonal reactivities of MNBN, a three-step cascade sequence, including nitrile cyclotrimerization, Knoevenagel condensation, and reductive cyclization, achieved the symmetrization, reticulation, and functionalization in one pot, thereby enabling the hierarchical construction of two series of COFs with stable o-nitrostyrene or indole linkages. The resulting COFs displayed high crystallinity, permanent porosity, and exceptional stability; solid-state nuclear magnetic resonance (SSNMR) experiments combined with selective isotopic-labeling synthesis further confirmed the high selectivity and controllability of the hierarchical assembly. Notably, the indole-linked COFs, featuring conjugated and electron-rich frameworks, displayed emergent photoelectronic properties and served as efficient, reusable catalysts in both metal-free photocatalytic and metallaphotoredox reactions. By hierarchically exploiting the intrinsic reactivity of a simple, unsymmetric molecule, this work bridges classical organic synthesis and cross-scale covalent assembly, achieving the programmable construction of stable, diversified, and functional COFs.

Abstract The development of encryption materials is essential to meeting the increasing demand for information security. However, the present materials are susceptible to duplication due to a finite numbers of crypto states. Here, we report one chemical method to expand anticounterfeiting information from discrete, finite states to continuous, infinite states in the temporal domain by regulating the chemical reactions of luminescent radicals with the assistance of image-analysis technology. Infinite cryptographic materials were fabricated with continuous dynamic luminescence processes by integrating reversible radical reactions into confined radical luminescent systems. The inherent chemical kinetics of active radical emitters can be converted to time-dependent emission curves, serving as unclonable keys with nearly infinite crypto states in the temporal domain. Fluorescent AIE molecules were then introduced to expand the color gamut, further enriching the encoding capacity. These infinite cryptographic materials offer a robust anticounterfeiting platform, providing novel pathways for high-level information-protection applications.

Abstract Anion-π+ photosensitizers (PSs) possess exceptional reactive oxygen species (ROS) generation and precise organelle targeting that could disrupt intracellular metabolic homeostasis and induce nonapoptotic cell death, offering unique advantages in overcoming immunosuppression. However, previous reports mainly focused on modifying the π+ core but often overlooked the crucial role of anions. Herein, we present a facile perfluoroalkyl anion strategy to modulate the fluorescence intensity and ROS generation capacity of anion-π+ PSs. Perfluorobutanesulfonate (PFB) anions with a single-sided perfluoroalkyl chain and bis(perfluorobutylsulfonyl)amide (BPFB) anions bearing double-sided perfluoroalkyl chains were employed to readily replace the hexafluoroantimonate (HFA) counterions in A/HFA and TPQ/HFA, yielding A/PFB, TPQ/PFB, A/BPFB, and TPQ/BPFB. Compared to the incorporated PFB anions, the BPFB anions more effectively restrict intramolecular motion through anion-π+ and van der Waals interactions, thereby significantly enhancing the fluorescence intensity of the phototheranostic agents─by 50.8-fold and 4.2-fold in A/BPFB nanoparticles (NPs) and TPQ/BPFB NPs compared to their HFA analogues, respectively. Concurrently, TPQ/BPFB NPs with second near-infrared emission demonstrated superior ROS generation, excellent mitochondrial targeting, and remarkable resistance to photobleaching. Strikingly, TPQ/BPFB NPs can activate both necroptosis and ferroptosis under irradiation, triggering a robust systemic immune response. Additionally, the lipophilicity granted by BPFB enables TPQ/BPFB NPs to infiltrate deeper into tumors, guaranteeing a more extensive photodynamic therapy with a 95% tumor suppression rate. Crucially, the immune memory triggered by TPQ/BPFB NPs effectively decreases the occurrence of lung metastases. Altogether, the perfluoroalkyl anion strategy proposed in this study offers new insights for developing potent anion-π+ PSs.

Abstract Polymer properties are profoundly impacted by tacticity, necessitating an understanding of the origins of stereocontrol to make high-performance materials. Recently, we reported that controlled incorporation of stereoerrors into trans-poly(3-hydroxy-2-methylbutyrate) (trans-PHMB) through the isoselective polymerization of rac-trans-3,4-dimethylpropiolactone (trans-DMPL) using racemic “sandwich” (BDI)Zn alkoxide complexes (where BDI = β-diketiminate) enables tuning of mechanical properties to match those of low-density polyethylene. However, the mechanism of stereocontrol of these catalysts was not explored. Herein, we report a thorough experimental and computational investigation uncovering a distinct manifestation of cooperative enantiomorphic-site and chain-end control, which we describe as site-mediated asymmetric chain-end control, where catalyst (Δ and Λ) and chain-end chiralities (R,R or S,S) work synergistically to influence the reaction’s stereoselectivity and rate. Experimental and computational data converge remarkably well, revealing that a Δ-catalyst with an (R,R)-chain end (Δ-RR) is isoselective 90% of the time. In contrast, a Δ-catalyst with an (S,S)-chain end (Δ-SS) is unselective. Detailed Density Functional Theory (DFT) investigations suggest molecular-level rationale for this mechanism of stereocontrol, demonstrating that chain positioning, monomer distortion, and ligand interactions work in conjunction to foster isoselectivity. Finally, DFT and kinetic modeling reveal that when polymerizing rac-trans-DMPL, the populations of Δ-RR and Δ-SS are equal and the high overall isoselectivity (mm% = 71–73%; where mm% is the percent of triads with a meso configuration across both ester linkages) of the catalyst is attributed to Δ-RR being faster than Δ-SS.

Abstract Modern catalysis research has primarily focused on improving catalyst activity, selectivity, and stability through active-site engineering, microenvironment regulation, and mechanistic understanding. However, the sustainability and efficiency of catalytic processes also depend on the dynamic evolution of reaction systems, including substrate consumption, catalyst deactivation, and product accumulation. Despite their importance, these changes are typically assessed by off-line analysis rather than real-time monitoring, which hinders efficient process optimization and sustainable operation. Here, we develop a dynamic self-reporting (DSR) catalytic system based on Ag@UiO-66-(COOH)2/NDCA that simultaneously functions as a heterogeneous oxidation catalyst and an optical reporter for reaction progress. During oxidation, the emission intensity at 440 nm increases with product formation and exhibits a strong quantitative correlation with benzaldehyde yield, enabling reaction progress to be continuously tracked across a series of substituted benzyl alcohols. Mechanistic studies indicate that the luminescence response is governed by competitive absorption and substrate-dependent interactions. Density functional theory calculations further reveal that benzyl alcohol forms stronger dispersion-stabilized π···π interactions with the emissive NDCA2– linkers than benzaldehyde, resulting in more pronounced luminescence quenching. As benzyl alcohol is converted into the more weakly interacting product, this quenching is progressively relieved, producing a measurable increase in emission intensity that reports the reaction progress. This integration provides a platform for reaction monitoring, process optimization, and future automated manufacturing.