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At least 73 records · Page 4

Electro-chemo-mechanically Driven Ni Exsolution from (Pr,Ce,Ni)O 2−δ : Controlled Nucleation Density and Enhanced Electrode Kinetics

In situ exsolution of metal nanoparticles is a promising strategy to prepare electrocatalysts with enhanced activity and resistance to agglomeration for efficient chemical transformations and energy conversion. Achieving a high nucleation density of nanoparticles under mild conditions and understanding how to tailor the process is important for performance of these electrodes in electrochemical cells. In this work, we demonstrate facile exsolution of Ni nanoparticles using fluorite-structured (Pr,Ce)O 2−δ as the support oxide, driven by electrochemical potential and aided by the metastability of Ni in the solid solution (elastic driving force). We prepare single-phase oriented thin films of (Pr,Ce,Ni)O 2−δ (NPCO) on (Zr,Y)O 2−δ (YSZ) substrates by pulsed laser deposition. With the aid of a high-throughput electrochemical cell that provides a lateral gradient in Nernst voltage, we apply in situ near-ambient pressure synchrotron X-ray photoelectron spectroscopy and ex situ atomic force microscopy to investigate the impact of electrochemical potential on Ni nucleation density. We find that metallic Ni can be successfully exsolved at 550 °C upon cathodic biasing in 20 mTorr O 2 , and its nucleation density increases with increasing electrochemical driving force/decreasing oxygen chemical potential. We further evaluate the electrochemical performance under highly reducing (fuel electrode) conditions by electrochemical impedance spectroscopy. With the exsolved Ni nanoparticles, the surface exchange coefficient of the NPCO is found to be ∼4× higher than for PCO without exsolution. This work confirms mixed conducting fluorites as beneficial host lattices for facile transition-metal exsolution and suggests the possibility for constructing an all ceria-based electrochemical cell with PCO serving as both the cathode and the anode.

36 MATERIALS SCIENCE

Graphene Quantum Dot Composites Embedded with CoZn Alloy Nanoparticles for Enhanced Oxygen Reduction and Evolution Reactions

Developing efficient and durable electrocatalysts for oxygen reduction (ORR) and oxygen evolution reactions (OER) is crucial for energy conversion technologies. In this study, core–shell graphene quantum dot (GQD) composites embedded with Co, Zn, and CoZn alloy nanoparticles were synthesized using a solid-state microwave synthesis method and systematically investigated for their electrochemical performance. The structural and compositional analyses confirm that the integration of transition metal nanoparticles enhances the electronic properties of GQDs, providing abundant active sites and facilitating charge transfer. Electrochemical characterization reveals that GQD-CoZn-3 (GQD:Co:Zn = 10.5:0.5:0.5) exhibits superior ORR and OER catalytic activities, achieving the highest current densities of 205 A g–1 and 102 A g–1 at 100 mV s–1, respectively. These performance values surpass those of pristine GQDs and single-metal (Co or Zn) embedded counterparts, emphasizing the strong synergistic effect between the CoZn alloy and the functionalized carbon framework. Impedance measurements further reveal a substantial reduction in charge-transfer resistance, while chronoamperometry tests demonstrate excellent catalytic stability and CO tolerance, highlighting the robustness of the core–shell GQD structure. These findings provide valuable insights into the design of advanced carbon-based electrocatalysts for energy applications.

Panda, Pradeep Kumar

Carbon nanodot precursors enable ultrahigh-loading copper single-atom catalysts for oxygen reduction reaction

Single-atom catalysts (SACs) have attracted significant attention in electrocatalysis due to their high metal utilization and tunable electronic structures; however, their practical implementation is often limited by poor atomic dispersion, low metal loadings (typically < 1 wt%), and insufficient anchoring of single metal atoms on catalyst supports. Herein, we report a simple and versatile strategy to synthesize copper single-atom catalysts (Cu-SACs) with ultrahigh metal loading using citric-acid-derived carbon nanodots as metal-capturing precursors. Through hydrothermal treatment followed by pyrolysis in the presence of urea, atomically dispersed copper atoms coordinated with nitrogen are incorporated into a carbon framework, achieving a Cu loading of up to 20 wt% while maintaining atomic dispersion. Notably, a significant fraction of the copper single atoms exists as Cu+–N2 coordination, which provides under-coordinated and catalytically active sites. The resulting Cu-SAC exhibits promising oxygen reduction reaction (ORR) activity in alkaline media, delivering a limiting current density comparable to that of commercial 20 wt% Pt/C with a predominant four-electron reduction pathway. Despite this high intrinsic activity, durability tests reveal gradual performance degradation under prolonged electrochemical operation, which is attributed to demetallation and aggregation of copper single atoms into metallic nanoparticles. These results demonstrate the potential of carbon nanodot-based platforms for synthesizing high-loading SACs, while underscoring the critical need to simultaneously control carbon porosity and metal–nitrogen coordination to enhance active-site accessibility and durability.

Sharma, Prakhar [University of Kentucky]

Identification of the glassy state in nanoparticles by transmission electron microscopy

Identification of amorphous phases in nanoparticles by atomic-resolution transmission electron microscopy (TEM) requires analyses such as tilt-angle-dependent TEM imaging and single-nanoparticle electron diffraction, rather than relying on a single TEM image. Here, the disordered structures of amorphous nanoparticles offer unique atomic configurations and properties that differ from the properties of their crystalline counterparts. These characteristics have motivated the exploration of such materials for mechanical, sensing and catalytic applications. In addition, the formation of amorphous metal nanoparticles is an important endeavour to understand the process of vitrification and the nature of the glassy state. Atomic-resolution transmission electron microscopy (TEM) is increasingly being used as a tool for characterizing structures of nanoparticles produced by vitrification. In this Comment, we discuss the pitfalls of using TEM for ascertaining whether nanoparticles are amorphous. We also make recommendations of best practices.

Alcorn, Francis M. [Sandia National Laboratories (

A Robust and Engineerable Self-Assembling Protein Template for the Synthesis and Patterning of Ordered Nanoparticle Arrays

Self-assembling biomolecules that form highly ordered structures have attracted interest as potential alternatives to conventional lithographic processes for patterning materials. Here we introduce a general technique for patterning materials on the nanoscale using genetically modified protein cage structures called chaperonins that self-assemble into crystalline templates. Constrained chemical synthesis of transition metal nanoparticles is specific to templates genetically functionalized with poly-Histidine sequences. These arrays of materials are ordered by the nanoscale structure of the crystallized protein. This system may be easily adapted to pattern a variety of materials given the rapidly growing list of peptide sequences selected by screening for specificity for inorganic materials.

McMillan, R. Andrew

Bio‐Inspired In Situ Tuning of the Hydrophobic Environment Around Catalytically Active Organic Ligand‐Stabilized Ruthenium Nanoparticles

Abstract The organic ligand environment surrounding enzymatic and homogeneous catalytic active sites often determines catalytic activity. Ruthenium nanoparticles, ≤1 nm in diameter, are synthesized using monodentate thiol, monodentate phosphine, and bidentate bisphosphine ligands. Even though some of the ruthenium surface is blocked by the ligands, catalytic activity is still observed for CO oxidation and H 2 O 2 decomposition. All three ligand‐stabilized ruthenium nanoparticles have similar CO oxidation rates; however, the bisphosphine‐stabilized Ru nanoparticles are approximately 2.5 times less active than the monothiol‐stabilized and monophosphine‐stabilized ruthenium nanoparticles for H 2 O 2 decomposition. It is observed that the organic ligand environment is modulated in situ during nanoparticle synthesis via partial oxidation of the bisphosphine as confirmed by 31 P NMR measurements. We hypothesize that bisphosphine‐bound Ru nanoparticles consist of a Ru core with some of the ligands bound in a monodentate manner where the other P atom is oxidized and not bound to the Ru surface leading to a thicker hydrophobic layer around the Ru nanoparticles. The increase in hydrophobicity is confirmed via contact angle and zeta potential measurements. H 2 O 2 decomposition rates are known to decrease with increasing hydrophobicity, and this work illustrates a pathway for increasing hydrophobicity in situ using ligand‐bound metallic nanoparticles.

Sufyan, Sayed Abu [Department of Chemical Engineer

Cascaded Photoenhancement: Implications for Photonic Chemical and Biological Sensors

Our analysis shows that coupling of gold nanoparticles to microspheres will evoke a cascading effect from the respective photoenhancement mechanisms. We refer to this amplification process as cascaded photoenhancement, and the resulting cavity amplification of surface-enhanced Raman scattering (SERS) and fluorescence as CASERS and CAF, respectively. Calculations, based on modal analysis of scattering and absorption by compound spheres, presented herein indicate that the absorption cross sections of metal nanoparticles immobilized onto dielectric microspheres can be greatly enhanced by cavity resonances in the microspheres without significant degradation of the resonators. Gain factors associated with CSP of 10(exp 3) - 10(exp 4) are predicted for realistic experimental conditions using homogenous microspheres. Cascaded surface photoenhancement thus has the potential of dramatically increasing the sensitivities of fluorescence and vibrational spectroscopies.

Fuller, Kirk A.

Radiation Shielding System Using a Composite of Carbon Nanotubes Loaded with Electropolymers

Single-wall carbon nanotubes (SWCNTs) coated with a hydrogen-rich, electrically conducting polymer such as polyethylene, receive and dissipate a portion of incoming radiation pulse energy to electrical signals that are transmitted along the CNT axes, and are received at energy-dissipating terminals. In this innovation, an array of highly aligned nanowires is grown using a strong electric field or another suitable orientation procedure. Polyethylene (PE), polymethymlethacrylate (PMMA), or other electrically conducting polymer is spin-coated onto the SWCNTs with an average thickness of a few hundred nanometers to a few tenths of micrometers to form a PE/SWCNT composite. Alternatively, the polymer is spin-coated onto the nanowire array or an anodized alumina membrane (AAM) to form a PE/metal core shell structure, or PE can be electropolymerized using the SWCNTs or the metal nanowires as an electrode to form a PE/SWCNT core shell structure. The core shell structures can be extruded as anisotropic fibers. A monomer can be polymerized in the presence of SWCNTs to form highly cross-linked PE/SWCNT films. Alternatively, Pb colloid solution can be impregnated into a three-dimensional PE/SWCNT nanostructure to form a PW/SWCNT/Pb composite structure. A face-centered cubic (FCC) arrangement provides up to 12 interconnection channels connected to each core, with transverse channel dimensions up to 20 nm, with adequate mechanical compressive strength, and with an associated electrical conductivity of around 3 Seimens/cm for currents ranging from 0.01 to 10 mA. This threedimensional nanostructure is used as a host material to house appropriate radiation shielding material such as hydrogen- rich polymer/CNT structures, metal nanoparticles, and nanowires. Thicknesses of this material required to attenuate 10 percent, 50 percent, and 90 percent of an incident beam (gamma, X-ray, ultraviolet, neutron, proton, and electron) at energies in the range of 0 440 MeV are being determined, for example, by measuring fluence rate reduction. For example, a radiation field arrives first at an exposed surface of the innovation and produces an associated first electric field within the metal-like fingers of the three-dimensional nanostructure. This field is intensified near the exposed tips of the fingers, and this intensified field generates an intensified second electric field near the adjacent exposed tips of the coated CNSs. This generates an associated electrical current in the CNSs, and the associated electropolymer coating. The current is received by the second substrate transport component and is transported to the dissipation mechanism located contiguously to the second substrate.

McKay, Chris

Quantum Theory of Surface Lattice Resonances

The collective interactions of nanoparticles arranged in periodic structures give rise to high‐ in‐plane diffractive modes known as surface lattice resonances. Although these resonances and their broader implications have been extensively studied within the framework of classical electrodynamics and linear response theory, a quantum optical theory capable of describing the dynamics of these structures, especially in the presence of material nonlinearities beyond ad hoc few‐mode approximations, is largely missing. To this end, we consider a lattice of metallic nanoparticles coupled to the electromagnetic field and derive the quantum input–output relations within the electric dipole approximation. As applications, we analyze coupling between the nanoparticle array and external quantum emitters, and show how the formalism extends to molecular optomechanics, where the high ‐factors of SLRs enable coupling to collective vibrational modes. We further consider arrays composed of saturable excitonic emitters, demonstrating how emitter nonlinearities can be used to switch the SLR condition between electronic transitions. Using a perturbative approach that accounts for population dynamics, we show how these effects can be probed in pump–probe experiments and give rise to nonlinear phase‐matching phenomena. Our work provides a microscopic framework for modeling SLRs interacting with quantum emitters without phenomenological descriptions of the electromagnetic environment.

molecular optomechanics

Nanopore-Templated Silver Nanoparticle Arrays Photopolymerized in Zero-Mode Wavelengths

In situ fabrication of nanostructures within a solid-polymer electrolyte confined to subwavelength-diameter nanoapertures is a promising approach for producing nanomaterials for nanophotonic and chemical sensing applications. The solid-polymerelectrolyte can be patterned by lithographic photopolymerization of poly(ethyleneglycol) diacrylate (PEGDA)-based silver cation (Ag+)-containing polyelectrolyte. Here, we present a new method for fabricating nanopore-templated Ag nanoparticle (AgNP)arrays by in situ photopolymerization using a zero-mode waveguide (ZMW) array to simultaneously template embedded AgNPs and control the spatial distribution of the optical field used for photopolymerization. The approach starts with an array of nanopores fabricated by sequential layer-by-layer deposition and focused ion beam milling. These structures have an optically transparent bottom, allowing access of the optical radiation to the attoliter-volume ZMW region to photopolymerize a PEGDA monomer solution containing AgNPs and Ag+. The electric field intensity distribution is calculated for various ZMW optical cladding layer thicknesses using finite-element simulations, closely following the light-blocking efficiency of the optical cladding layer. The fidelity of the polyelectrolyte nanopillar pattern was optimized with respect to experimental conditions, including the presence or absence of Ag+ and AgNPs and the concentrations of PEGDA and Ag+. The self-templated approach for photo patterning high-resolution photolabile polyelectrolyte nanostructures directly within a ZMW array could lead to a new class of metamaterials formed by embedding metal nanoparticles within a dielectric in a well-defined spatial array.

Zero-mode waveguide

pH‐Mediated Strong Metal‐Support Interaction Construction Through Dynamic Fermi Level Tuning

The metal–support interface is central to governing catalytic transformations. While strong metal–support interaction (SMSI) is an established strategy to tailor the morphology and electronic properties of supported metal catalysts, the role of interfacial charge redistribution in SMSI formation remains poorly understood and rarely leveraged. Here, in this study, we report a dual-stimuli approach that combines pH modulation with ultrasonication to mediate SMSI construction in aqueous solution through dynamic Fermi level tuning. By leveraging in situ pH-driven charge redistribution at the metal–support interface, we achieve controllable SMSI encapsulation of metal nanoparticles, as verified by electrochemical analysis, work function measurements, and x-ray-based techniques. The resulting catalysts exhibit tunable SMSI features and deliver enhanced activity and selectivity in hydrogenation reactions. This work establishes a facile strategy to modulate catalyst structure and electronic properties by exploiting Fermi level variation as a driving force, thereby advancing rational SMSI design and catalytic performance across diverse environments.

77 NANOSCIENCE AND NANOTECHNOLOGY

Recent Progress on Cerium Oxide‐Based Nanostructures for Energy and Environmental Applications

Cerium oxide (CeO 2 ) photo/electrocatalysts for energy storage and environmental applications have attracted considerable interest because of stable crystal structure, low toxicity/cost, superior chemical stability, stable redox (Ce 3+ /Ce 4+ ) pairs, abundant oxygen defects, and capablility for intense interaction with other materials. However, the wide bandgap and poor conductivity lower the CeO 2 photo/electrocatalytic and energy storage performances. To overcome these limitations, various modification strategies (tuning morphology, doping or loading of metal nanoparticles, and heterostructures) have been applied for the improvement of photocatalytic (removal of organic contaminants from water/wastewater and H 2 production and CO 2 reduction reactions) efficiency, electrocatalytic (hydrogen/oxygen evolution reactions and CO 2 reduction reactions), and energy storage performances (supercapacitor) of CeO 2 ‐based materials. Herein, the recent progress of CeO 2 ‐based materials for electro(photo)catalysis and energy storage applications has been discussed. The challenges and possible direction of CeO 2 ‐based materials for electro(photo)catalysis and energy storage applications have been emphasized. Furthermore, this comprehensive review is expected to advance the design of CeO 2 ‐based materials and their applications in electro(photo)catalysis and energy.

Ray, Schindra Kumar [Department of Chemistry North

Self‐Limiting Polymerization‐Induced Crystallization‐Driven Self‐Assembly (SL‐PI‐CDSA) Enables Templated Synthesis of Chiral Plasmonic, Hybrid 2D Hexagonal Assemblies

Examples of self-regulating synthetic self-assembly are relatively few, with most known chemical systems relying on kinetic rather than thermodynamic control. Herein, we demonstrate the rapid generation (t ≤ 5 min) of size-tunable ultralow dispersity (Ð ≤ 1.01) 2D hexagonal nanosheets governed by self-limiting self-assembly (SLSA). Self-assembly in natural systems occurs with exquisite control of structure, function, and dimension. We demonstrate that key aspects of biological assembly can be rationally applied toward the development of bottom-up approaches for the construction of chiral nanomaterials. To this end, self-limiting polymerization-induced crystallization-driven self-assembly (SL-PI-CDSA) of modular and templating aryl isocyanide (AIC) monomers yields functional 2D assemblies permitting post-polymerization/assembly modifications. Detailed study of the internal and external structure of the hexagonal nanosheets reveals topological defects which offer mechanistic insights into both their assembly and subsequent utilization. Specifically, these features enable fabrication of chiral hybrid organic–inorganic nanomaterials incorporating chiral plasmonic metal nanoparticles (MNPs). Our results suggest that the synergistic interplay of template-driven confinement and hierarchical chirality induce symmetry breaking of in situ-generated gold MNPs. We anticipate that the platform presented will facilitate fabrication of new hybrid, chiral organic–inorganic nanostructures.

36 MATERIALS SCIENCE

Autonomous Aerosol and Plasma Co‐Jet Printing of Metallic Devices at Ambient Temperature

Abstract Additive manufacturing of metallic materials holds the potential to revolutionize the fabrication of functional devices unattainable via traditional methods. Despite recent advancements, printing metallic materials typically requires thermal processing at elevated temperatures to form dense structures with desired properties, which presents a major challenge for direct printing and integration with temperature‐sensitive materials. Herein, a unique co‐jet printing (CJP) method is reported integrating an aerosol jet and a non‐thermal, atmospheric pressure plasma jet to enable concurrent aerosol deposition of metal nanoparticle inks and in situ sintering at ambient temperature. A machine learning algorithm is integrated with the CJP to perform real‐time defect detection and autonomous correction, enhancing the yield of printed films with high electrical conductivity from 44% to 94%. Concurrent printing and sintering eliminate the need for post‐printing processing, reducing the overall manufacturing time by multiple folds depending on product size. CJP enables direct printing of functional devices on a variety of temperature‐sensitive materials including biological materials. Direct printing of hydration sensors on living plant leaves is demonstrated for long‐duration monitoring of hydration level in the plant. The versatile CJP method opens tremendous opportunities to harmoniously integrate abiotic and biotic materials for emerging applications in wearable/implantable devices and biohybrid systems.

Du, Yipu [Department of Aerospace and Mechanical E

Enhanced Laser-Induced Graphene Microfluidic Integrated Sensors (LIGMIS) for On-Site Biomedical and Environmental Monitoring

The convergence of microfluidic and electrochemical biosensor technologies offers significant potential for rapid, in-field diagnostics in biomedical and environmental applications. Traditional systems face challenges in cost, scalability, and operational complexity, especially in remote settings. Addressing these issues, laser-induced graphene microfluidic integrated sensors (LIGMIS) are presented as an innovative platform that integrates microfluidics and electrochemical sensors both comprised of laser-induced graphene. This study advances the LIGMIS concept by resolving issues of uneven fluid transport, increased hydrophobicity during storage, and sensor biofunctionalization challenges. Key innovations include Y-shaped reservoirs for consistent fluid flow, hydrophilic polyethyleneimine coatings to maintain wettability, and separable microfluidic and electrochemical components enabling isolated electrode nanoparticle metallization and biofunctionalization. Multiplexed electrochemical detection of the neonicotinoid imidacloprid and nitrate ions in environmental water samples yields detection limits of 707 nm and 10 -5.4 m with wide sensing ranges of 5–100 µm and 10 -5 –10 -1 m, respectively. Similarly, uric acid and calcium ions are detected in saliva, demonstrating detection limits of 217 nm and 10 -5.3 m with sensing ranges of 10–50 µm, and 10 -5 –10 -2.5 m, respectively. Overall, this biosensing demonstrates the capability of the LIGMIS platform for multiplexed detection in biologically complex solutions, with applications in environmental water quality monitoring and oral cancer screening.

environmental monitoring

Simulation of 24,000 Electron Dynamics: Real-Time Time-Dependent Density Functional Theory (TDDFT) with the Real-Space Multigrids (RMG)

Here, we present the theory, implementation, and benchmarking of a real-time time-dependent density functional theory (RT-TDDFT) module within the RMG code, designed to simulate the electronic response of molecular systems to external perturbations. Our method offers insights into nonequilibrium dynamics and excited states across a diverse range of systems, from small organic molecules to large metallic nanoparticles. Benchmarking results demonstrate excellent agreement with established TDDFT implementations and showcase the superior stability of our time integration algorithm, enabling long-term simulations with minimal energy drift. The scalability and efficiency of RMG on massively parallel architectures allow for simulations of complex systems, such as plasmonic nanoparticles with thousands of atoms. Future extensions, including nuclear and spin dynamics, will broaden the applicability of this RT-TDDFT implementation, providing a powerful toolset for studies of photoactive materials, nanoscale devices, and other systems where real-time electronic dynamics is essential.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Overcoming Variability: A Reproducible Approach to SERS Detection of Nanodiamonds

Detonation nanodiamonds (DNDs) are formed at specific pressures and temperatures during explosions. Different explosives produce varied yields of DNDs within their detonation soot, with Composition B producing the highest yield. Raman spectroscopy (RS) is often used for the characterization of sp 2 - and sp 3 -hybridized carbon allotropes in carbonaceous materials because of distinct disorder and graphitic bands. Bulk diamond also gives a distinct Raman peak at 1332 cm –1 . Furthermore, as bulk diamond decreases in size to nanometer-sized species, the peak red-shifts and broadens, becoming increasingly difficult to detect with RS using visible excitations. Therefore, surface-enhanced Raman spectroscopy (SERS) was used to enhance the diamond peak of DNDs, enabling better detection and faster examination of DNDs within detonation soot. Previous literature of the SERS of DNDs delivered inconsistent results in spectral signatures and SERS substrates. Herein, refining of the methodology for the acquisition of SERS spectra of DNDs was achieved. Before any SERS experiments, the DNDs were first characterized with normal Raman (NR) and scanning electron microscopy. Two routes for SERS enhancement were evaluated: colloidal noble metal nanoparticles and evaporated silver films. Silver films produced the best signal enhancement of DNDs with the best signal-to-noise and peak enhancements observed at 20–30 nm thick silver films at 5% (∼300 μW) laser power. Consistent, reproducible SERS spectra were acquired of small aggregates of DNDs down to ∼500 nm. NR and SERS mapping analysis of DNDs before and after evaporation of silver films revealed the improvements in the detection capabilities of SERS compared with NR.

Carbon

Catalytic Triad-Inspired Nanozyme Catalysts for Ester Hydrolysis in Organic Solvent Mixtures

We synthesized a series of molecular nanozyme catalysts containing functional groups (imidazole, carboxylic acid, and hydroxyl groups) inspired by the catalytic triad found in natural serine hydrolases. Different structural features were incorporated using two distinct synthesis routes to investigate the influence of interactions beyond the active site on catalytic activity in designing molecular nanozymes. Molecular dynamics simulations suggest that nanozyme activity is affected by structural features that influence nanozyme hydrophilicity and the organization of the local solvent environment. The most active nanozyme showed activity comparable to the enzyme α-chymotrypsin for the hydrolysis of a model ester (4-nitrophenyl 4- hydroxybenzoate) in a 95:5 (v/v%) water/acetonitrile mixture at ambient temperature. Increasing the temperature and organic solvent content decreases the activity of α-chymotrypsin while enhancing the activity of the nanozymes. The nanozymes can be immobilized on supported metal nanoparticles using a dithiol self-assembled monolayer, which facilitates their removal from the postreaction solution. These results demonstrate the potential in creating solvent-tolerant bioinspired catalysts, thereby combining the advantages of biocatalysts and chemical catalysts as next-generation industrial catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH