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ENCYCLOPEDIA OF EARTH AND ATMOSPHERIC SCIENCES ENCYCLOPEDIA OF MATHEMATICAL SCIENCES ENCYCLOPEDIA OF BIOLOGICAL,PHYSIOLOGICAL AND HEALTH SCIENCES ENCYCLOPEDIA OF SOCIAL SCIENCES AND HUMANITIES ENCYCLOPEDIA OF PHYSICAL SCIENCES,ENGINEERING AND TECHNOLOGY RESOURCES ENCYCLOPEDIA OF CHEMICAL SCIENCES,ENGINEERING AND TECHNOLOGY RESOURCES ENCYCLOPEDIA OF WATER SCIENCES,ENGINEERING AND TECHNOLOGY RESOURCES ENCYCLOPEDIA OF ENERGY SCIENCES,ENGINEERING AND TECHNOLOGY RESOURCES ENCYCLOPEDIA OF ENVIRONMENTAL AND ECOLOGICAL SCIENCES,ENGINEERING AND TECHNOLOGY RESOURCES ENCYCLOPEDIA OF FOOD AND AGRICULTURAL SCIENCES,ENGINEERING AND TECHNOLOGY RESOURCES ENCYCLOPEDIA OF HUMAN RESOURCES POLICY AND MANAGEMENT ENCYCLOPEDIA OF NATURAL RESOURCES POLICY AND MANAGEMENT ENCYCLOPEDIA OF DEVELOPMENT AND ECONOMIC RESOURCES ENCYCLOPEDIA OF INSTITUTIONAL AND INFRASTRUCTURAL RESOURCES ENCYCLOPEDIA OF TECHNOLOGY,INFORMATION, AND SYSTEMS MANAGEMENT RESOURCES ENCYCLOPEDIA OF REGIONAL SUSTAINABLE DEVELOPMENT REVIEWS

The above simplified figure illuminates the essential interconnectedness of the sixteen component encyclopedias of EOLSS.

 In the real world, the various knowledge domains do not exist in isolation from each other. They form an integrated whole, with links in all directions. It is well known that all forms of human knowledge are inter-connected and inter-related. EOLSS mimics this complexity, the automatic inter-connectedness of the various subject categories facilitating navigation through the vast landscape of EOLSS knowledge. This provides the user with an effective and efficient tool to search, navigate and browse through each of the component encyclopedias, through any combination of the sixteen, or through the whole of EOLSS.

ENCYCLOPEDIA OF CHEMICAL SCIENCES, ENGINEERING AND TECHNOLOGY RESOURCES

CONTENT OUTLINE (partial listing)

 

INORGANIC AND BIOINORGANIC CHEMISTRY

Chemical Elements and their Discovery

Determining the Name of Chemical Elements

Abundance of Elements on Earth

Periodic Table

Periodic Trends of Groups and Periods

The Inorganic Chemical Industry

Sources of Inorganic Raw Materials

The Beginnings

Sulfuric Acid

Nitrogen Compounds

Phosphoric Acid

Chlor-alkali Compounds

Oxygen Compounds

 

FROM SIMPLE TO COMPLEX COMPOUNDS

Metal amine complexes: bonding and geometry

Metal complexes of multidentate ligands: deviations from regular geometries

Linkage isomerism: the nitro-nitrito interconversion

Multidentate ligands with more sophisticated shapes: rings and cages

The metal template synthesis of macrocycles

The metal template synthesis of catenanes

Self-assembling driven by metal centres: helicates and grids

Coordination assemblies made on PdII building blocks

The coordination chemistry of anions

 

CHEMISTRY OF METALS

Structural and physical properties of metals

General aspects of extracting metallurgy

Historical background

Extracting metallurgy

Alloying behavior

Introduction

Phase diagrams

Real phase diagrams

Qualitative prediction of alloying behaviour

Intermetallic phases

Introduction

Identification of intermetallic phases

Terminal (or primary) solid solutions

Superlattices

Metastable solid solutions

Intermetallic compounds

Synthesis of intermetallic phases

Uses of intermetallic phases

 

INORGANIC SYNTHESIS

Coordination compounds: generality

Werner complexes

Organometallic complexes

Metal carbonyls

Binary cyclopentadienyl derivatives

Metal arene derivatives

Coordination compounds: reactivity

Substitution reactions

Redox reactions

Oxidative addition / Reductive elimination.

Insertion reactions

 

RADICAL REACTIONS WITH METAL COMPLEXES IN AQUEOUS SOLUTIONS

Radicals and their role in chemical processes with emphasis on biological systems

The chemistry of radicals

Initiation, Propagation, Termination

Formation of Radicals

Redox Properties of Radicals

Detection of Radicals   

Important types of Radicals

Inorganic Radicals

Hydroxyl Radicals

Superoxide Radicals

Dihalogen Radicals

Sulfur Oxide Radicals

Organic Radicals

Aliphatic Carbon Centered Radicals

Aliphatic Peroxyl Radicals

Thyil Radicals

Stable Radicals

Dioxygen

Nitrogen Oxide , Nitrogen Dioxide

Organic Radicals, e.g. Antioxidants, Nitroxides, Methylviologen, DPPH   

The Role of transition metal complexes in radical chemistry

Reactions with Aliphatic and Aliphatic Peroxyl Radicals

Reactions with Aliphatic Radicals

Redox Reactions of Radicals with Transition Metal Complexes

Formation of Transition Metal Complexes with Metal-carbon σ-bonds.

Reactions with Aliphatic Peroxyl Radicals

Fenton-like Reactions

Transition Metal Complexes with Ligand Radicals

 

MAGNETIC AND OPTICAL PROPERTIES

Electronic structure of Transition Metal ions

Free ion

Coordination complexes

The ligand field approach

Principles of optical spectroscopy

Rationalization of Uv-Vis spectra

Optical properties of polynuclear species

The spin Hamiltonian formalism

Magnetic properties of metal complexes

First transition row

Second-third transition row

Magnetism of rare earth ions

Magnetism of polynuclear systems

Highlights of recent research breakthroughs

 

INORGANOMETALLIC CHEMISTRY

Definition of inorganometallic vs. organometallic chemistry

Inorganometallic compounds containing transition metal (TM)- main group metal (E) bond - synthesis, structure and reactivity

Inorganometallic complexes of TM with group 13 elements

Inorganometallic complexes of TM with boron

Inorganometallic complexes of TM with heavier elements of group 13

Inorganometallic complexes of TM with group 14 elements

Inorganometallic complexes of TM with group 15 elements

Inorganometallic complexes of TM with group 16 elements

Inorganometallic clusters

Inorganometallics and catalysis

Special applications of TM-E compounds

Inorganometallics as precursors of optoelectronic materials

Inorganometallic ceramics

 

HIGH TEMPERATURE MATERIALS AND SOLID STATE CHEMISTRY

Importance of solids

Crystalline solids

Chemical classification of solids

Covalent solids

Ionic solids

Metallic solids

Molecule-based solids

Bonding in solids

Introduction

Band theory

Metals, semiconductors and insulators

Electrical behavior of metal depending on temperature

Optical Properties of Solids

Superconductors

Properties and technological applications

Defects in solids

Selected classes of inorganic solids

Hybrid Organic-Inorganic Layered perovskite halides

Inorganic materials for lithium-ion batteries

Inorganic and molecular superconductors

Multifunctional organic-inorganic hybrid solids

High Temperature Materials

Method of synthesis

 

INORGANIC BIOCHEMISTRY

Historical background

The philosophy of model chemistry

The role of metal cofactors

The metals of biology

Iron

Zinc

Copper

Molybdenum and tungsten

Nickel

Vanadium

Alkali and alkaline earth cations

The role of special metal cofactors

Tetrapyrroles

Hemes

Chlorophylls

Corrins

Coenzyme F430

Metalloclusters

Iron-sulfur clusters

Complex metalloclusters

Metalloclusters in nitrogenases

Metalloclusters in hydrogenases

Metalloclusters in nitrous oxide reductase

The metallocluster of the oxygen-evolving center of photosystem II

Metalloclusters in carbon monoxide dehydrogenase/acetyl coenzyme A synthase

 

INORGANIC REACTION MECHANISMS

Introduction

Historical background.

Planning a mechanistic study

Kinetic techniques.

Probing a reaction mechanism.

A classification of inorganic reactions

Ligand substitution reactions

Langford -Gray classification of mechanisms.

Ligand substitution at square planar-complexes.

The kinetics and mechanism of substitution.

The stereochemistry of the substitution.

Nucleophilicity scale for platinum (II).

The trans – effect

The dissociative mechanism for substitution.

Ligand substitution at octahedral complexes.

Ligand replacement  on hexaaqua ions.

Complex formation. The Eigen-Wilkins mechanism.

Solvolysis Reactions on Co(III) Amine Complexes.

Stereochemistry of Octahedral Substitution.

Base hydrolysis and the SN1CB mechanism on CoIII amine complexes.

Stereochemical nonrigidity of ligands.

Geometrical Isomerization of Square-Planar Complexes.

Redox reactions.

Inner-sphere mechanism.

Outer-sphere Reactions.

 

CLUSTERS AND POLYNUCLEAR COMPOUNDS

Introduction: The ubiquity of cage compounds in the Periodic Table and the relationships between molecular compounds and condensed phases.

Clusters of the p-block elements

Clusters of p-block elements in a ligand shell: Boron hydrides

Clusters in a ligand shell of the heavier elements of group 13 and 14

Bare clusters of p-block elements

Clusters of d-block elements

Low-valent Metal Clusters

Metal Carbonyl Clusters

Homometallic Metal Carbonyl Clusters

Metal carbonyl clusters containing interstitial main group heteroatoms

Mixed-metal carbonyl clusters

Phosphine-substituted Carbonyl Metal Clusters

Bonding in Metal Carbonyl Clusters

Properties and Applications of Metal Carbonyl Clusters

Low valent metal clusters stabilized by other σ−π ligands

Clusters of late transition metals stabilized by phosphines: The thin border between clusters and colloids

High-valent Metal Clusters

Halide Clusters of Early Transition Metals

Polynuclear Compounds

Polyoxometallates and related compounds

Polynuclear compounds of transition and post-transition metals with bridging and polydentate ligands

 

STRUCTURE AND BONDING IN INORGANIC CHEMISTRY

Introduction 

Ligand-field Theory for Octahedral Complexes 

d–d Transitions

Factors that influence the value of D o

Ligand-field Theory for Square Planar Complexes 

Ligand-field Theory for Tetrahedral Complexes  

Charge-Transfer Absorption Bands   

Stabilities of Complexes 

Current Work and Further Reading  

 

 SYNTHESIS AND SPECTROSCOPY OF TRANSITION METAL COMPLEXES

Synthesis of Transition Metal Complexes

Spectroscopy of Transition Metal Complexes

Synthesis by Substitution Reactions

Synthesis by Oxidation/Reduction Reactions

Synthesis by Addition Reactions

Synthesis by Dissociation Reactions

Synthesis by Reaction of Coordinated Ligands

Synthesis by Self-assembly

Synthesis by Second Sphere Coordination

Spectroscopy of Transition Metal Complexes

Electronic Absorption Spectroscopy

Intensity of the Electronic Transitions

Polarized Electronic Absorption Spectroscopy

Charge Transfer Transitions

Selected Examples of d-d Electronic Absorption Spectra

Electronic Absorption Spectra of Complexes of d1, d4, d6, and d9 ions

Electronic Absorption Spectra of d2, d3, d7, and d8 ions

Electronic Absorption Spectra of Complexes of d5 ions

Electron Paramagnetic Resonance Spectroscopy (EPR,ESR)

Basic Principles

CW-EPR

Multiple Resonance Spectra

Pulsed EPR

Spin-Hamiltonian and the Interpretation of the Spectra

Zeeman Interaction

Electron-Electron (Fine) Interaction

Electron-Nucleus (Hyperfine) Interaction

Selected Examples of EPR Spectra

Mössbauer Spectroscopy (MB)

Basic Principles and Applications

 

NANOSYSTEMS

Introduction

Distinctive features of nanosystems

General aspects of synthesis

Top-down approach

Bottom-up approach

Zero-dimensional nanosystems

Transition metal nanoparticles

Supported metal nanoparticles

Magnetic nanoparticles

Nanopowders

One-dimensional nanosystems

Nanowires and nanorods

Nanotubes

Two-dimensional nanosystems

Two-dimensional nanocrystals

Nanofilms

Nanomembranes

Two-dimensional arrays of 1-D and 0-D systems

Three-dimensional nanosystems

Three-dimensional nanocrystals

Three-dimensional superstructures

Nanoporous materials

Inorganic-organic hybrid nanosystems

Nanosystems in biochemistry

 

COMPUTATIONAL INORGANIC CHEMISTRY

General Considerations

The Fundamental Relation between Structure and Energy

Basic Computational Tools

The Molecular Mechanics Approach

Applications of the MM Method and Problems with Transition Metal Complexes

Foundations of the Quantum Mechanical Approach

The Hartree-Fock Method

Basis Sets

Methods of the Electron Correlation

Density Functional Theory (DFT)

QM Approach to Inorganic and Transition Metal Compounds

QM/MM Methods

Most Popular Software Packages

Goals and Strategies of Computational Methods

Selection of the Starting Model

SCF and Structure Optimization Procedures

Calculation of the Frequencies

Finding Transition Structures 

Derivation of Molecular Properties

Chemical Bonding

Mulliken Population Analysis

Other Population Analysis Schemes

Electrostatic Charges

Electric Multipole Moments

Electron Affinity and Ionization Potential

Non Linear Optical Properties (NLO)

ESR Hyperfine Coupling Constants

NMR spectral Properties

Magnetic Properties

Types of Chemical Information from MO Calculations

Characterization of New Chemical Species

Characterization of Species in Solution

Analysis of Fluxionality

Chemical Reactivity

MO Architectures

The Role of Symmetry

Concepts of Perturbation Theory

Correlation or Walsh Diagrams

Interaction Diagrams and Electron Counting Principles

Derivation of Fragment Molecular Orbitals and Isolobal Analogy Concept

Electron Counting and Metal-Metal Bonding in Transition Metal Clusters

Bonding between Metals and Organic Polyenes

MO Undepinnings of Oxidative Addition and Reductive Elimination Processes

Energy Partitioning Analysis and Bond Dissociation Energy

Molecular Dynamics

The Car-Parrinello Method

Solids and Surfaces

Cluster Calculations

Band Structures

Surfaces and Chemisorption

Computer Programs for Extended Structures

Analysis of the Electron Density (QTAIM Methods)

 

ENERGY AND INORGANIC CHEMISTRY

General background

Electronic excited states

Classification of excited states in coordination complexes  

Electron transfer processes

Energy transfer processes

Semiconductor materials

Molecular level energy conversion devices

Functions from natural photosynthesis

Photoinduced charge separation

Antenna effect

Supramolecular systems as photochemical molecular devices

Multielectron redox catalysts 

Inorganic photovoltaics

Silicon solar cells

Thin film solar cells

Multijunction and tandem cells

Solar concentrators

Photoelectrochemical solar cells

Sensitization of wide band-gap semiconductors.

Solar cell efficiency

Inorganic molecular sensitizers

Inorganic supramolecular sensitizers

Photoelectrochemical hydrogen production

Photoassisted electrolysis

Tandem solar cells

Conclusion

 

ORGANIC AND BIO-MOLECULAR CHEMISTRY

The Carbon atom

The carbon atom building blocks: hybridizations

Single and multiple bonds

Structure of organic compounds

Graphical representation of the structures of organic compounds

Different shapes that a molecule can assume: conformations

Asymmetry of some organic molecules: chirality and stereoisomers

Classification of organic compounds, the functional groups

Alkanes

Alkenes

Alkynes

Aromatic hydrocarbons

Haloalkanes

Alcohols

Thiols

Ethers

Thioethers, disulfides and trisulfides

Amines

Aldehydes and ketones

Carboxylic acids, esters and amides

Attractive interactions and molecular recognition

Reactivity of organic compounds

Molecules of life

Carbohydrates

Amino acids, peptides and proteins

Nucleic acids

Lipids

Fats, oils and waxes

Phospholipids and glycolipids

Terpenoids

Fat-soluble vitamins

Steroids

Organic compounds in the market

Dyes

Compounds for health care

Compounds for food industry

Polymers

Isolation, purification and analysis of organic compounds

 

ORGANIC SUBSTANCES AND STRUCTURES NOMENCLATURE OF ORGANIC COMPOUNDS

Type(s) of Nomenclature Operations

Substitutive Operation

Replacement Operation

Additive Operation

Conjunctive Operation

Subtractive Operation

Ring Formation or Cleavage

General Rules

Capitalized and Italic

Numbers of Position

Punctuation

Parent Name

Alkanes

Unsaturated Alkanes

Substituent Prefix Names Derived from Parent Hydrides

Functional Groups

Specific Classes of Compounds

Organometallic Compounds

Halogen Compounds

Nitrogen Compounds

Amines and Imines

Amides and Imides

Nitrile, Isocyanide and their Derivatives

Nitro and Nitroso Compounds

Azo, azoxy, diazo, and related compounds

Azides

Hydroxy Compounds and Analogues

Alcohols and Phenols

Substituent Prefixes Derived from Alcohols, Phenols, and their Analogues

Salts

Ethers

Cyclic Ethers

Aldehydes

Ketones

Ketenes

Acetals, Hemiacetals, Acylals, and their Analogues

Nitrogenous Derivatives of Carbonyl Compounds

Acids and Derivatives

Numbering of some Heterocyclic Rings

Numbering of Multiple Ring Systems

Name Construction

Rules

Examples

 

STEREOCHEMISTRY

Symmetry

Molecular models and symmetry evaluation

Symmetry elements and symmetry operations

Point groups

Chirality

Pairwise relationships between isomeric molecules

Topicity relationships among atoms and groups of atoms in molecules

Chirotopicity

Stereogenicity

On the distinction between chirality and stereogenicity

Conformation and configuration

Conformation

Configuration

Some considerations on the use of the terms conformation and configuration

Configurational descriptors

Dependence of the properties of chiral molecules on the enantiomeric composition

Racemic forms and enantiomerically pure compounds

Optical activity

Racemization

How to obtain stereoisomerically pure compounds

Separations

Stereoselective transformations

Reactions involving chiral non-racemic substrates and achiral reagents

Reactions involving chiral non-racemic reagents and achiral substrates

Reactions involving chiral substrates and reagents

Kinetic resolution

Multiple stereoselection

 

SYNTHETIC ORGANIC CHEMISTRY

Introduction

Definition and story of Synthetic Organic Chemistry

Target oriented synthesis

Method oriented synthesis

Synthetic strategy

Retrosynthetic analysis

Disconnections

One functional group disconnections

Two functional group disconnections

Disconnections of 1,2 dioxygenated structures

Disconnections of 1,3 dioxygenated structures

Disconnections of 1,4 dioxygenated structures

Disconnections of 1,5 dioxygenated structures

Disconnections of 1,6 dioxygenated structures

Protection and deprotection

Temporary and permanent protective groups

Protection of alcohols

Esters

Ethers

Silyl ethers

Acetals

Protection of diols

Protection of Amines

Carbamates

Amides

Azides

Protection of Aldehydes and Ketones

Protection of Carboxylic acids

Control of stereochemistry

The chiral pool approach

Stereoselective transformation

Chiral auxiliary

Chiral catalyst

Enzymes as chiral catalysts

The convergent strategy

Solid phase synthesis

Solid supports

Linkers and spacers

Acid-labile linkers

Base-labile linkers

Linkers cleaved by oxidation

Photo cleavable linkers

Silicon linkers

Metal-Assisted cleavages

Combinatorial synthesis

Environmental friendly synthetic procedures

Reaction media

Excess of reagents

Atomic economy

 

ORGANIC CHEMISTRY AND BIOLOGICAL SYSTEMS -BIOCHEMISTRY

From molecules to living systems: complexity is obtained from simple building blocks

Amino acids and proteins

Proteogenic amino acids

Non proteinogenic amino acids

Amino acid polymers: proteins. Their structure and function

Proteins folding and structure

Proteins function and regulation

Nucleotides and nucleic acids: information, energy transport, catalysis

Chemical structures of nucleotides

Nucleotide polymers: RNA and DNA

The flow of genetic information

DNA: storage and transmission of information

RNA: expression of information and catalysis

Nucleotides derivatives and coenzymes

Sugars : energy, structures, modulation of proteins properties

Monosaccharides and polysaccharides

Structural support and intracellular storage of fuel for cell metabolism

Effects of glycans on glycoproteins properties

Sugars as sources of energy and metabolic intermediates

Lipids: energy, membranes, protein targeting and signal transduction

Structures of lipids common in biochemistry

Lipids in cell metabolism

Lipids as the constituents of cell membranes

Lipid tails target proteins to membranes

 

CHEMISTRY OF NATURAL COMPOUNDS

Chemistry of natural products: a general perspective

Alkylation reactions

Nucleophilic substitution

Electrophilic addition

Wagner-Meerwein rearrangements

Aldol and Claisen reactions

Imine formation and the Mannich reaction

Transamination reactions

Decarboxylation reactions

Decarboxylation of a-amino acids

Decarboxylation of b-keto acids

Decarboxylation of a-keto acids

Oxidations and reductions

Dehydrogenases

Oxidases

Oxygenases

Amine oxidases

Carbohydrate processing enzymes: glycosidases and glycosyl transferases

Lipids

Hydrolizable lipids

Waxes

Triglycerides

Phospholipids

Non-hydrolizable lipids

Fat-soluble vitamins

Eicosanoids

Terpenoids

Steroids

Amino acids, peptides and proteins

Amino acids: structural features and acid-base behaviour

Amino acid biosynthesis

Peptides and proteins

Ribosomal biosynthesis of peptides and proteins

Nonribosomal biosynthesis of peptides and proteins

Relevant peptides and proteins

Hormones

Interferons

Opioid peptides

Enzymes

Nucleosides, nucleotides and nucleic acids

Purine nucleotides biosynthesis

Pirimidine nucleotides biosynthesis

Carbohydrates

Monosaccharides

Disaccharides, oligosaccharides, polysaccharides and carbohydrate processing enzymes

Glycoconjugates

Glycoproteins

Glycolipids

 

CHEMISTRY OF NUTRACEUTICS, FLAVOURS, DYES AND ADDITIVES

Flavors

Natural flavors

Flavors derived from lipid catabolism

Flavors of the terpene family

Flavors derived from amino acids catabolism

Artificial flavors

Dyes

Natural colorings

Carotenoids

Anthocyanins

Chlorophyll

Betalaines

Carminic acid and Curcumin

Synthetic dyes

Additives

Sweeteners or edulcorants

Nutritive sweeteners

Non-nutritive sweeteners

Preservatives

Main food spoilage

Antioxidants

Antimicrobials

Emulsifiers and stabilizers

Nutraceutics

Flavonoids

Polyunsaturated fatty acids (PUFAs)

Amino acids

Vitamins

 

Organic Photochemistry

Photophysics: interaction of light with matter and photostimulated processes.

Interaction with atoms

Interaction with molecules

Photophysical processes

Photochemistry

Photochemical processes

Organic photostimulated reactions.

Dissociation into radicals

Dissociation into ions or “internal” electron transfer

Intramolecular rearrangement

Photoisomerization

Hydrogen atom abstraction

Photodimerization or photoaddition

Photosensitized reactions

Photoionisation reactions

Miscellaneous

Photoreactivity of aromatic compounds

Photochemistry of diazo- and azido compounds

Photocleavable protecting groups

Photopolimerization

Chemoluminescence

Technical and experimental aspects.

 

ORGANOMETALLIC CHEMISTRY

Organometallic compounds of the groups IA, IIA, and IIB

Organolithium compounds

Preparation of organolithium compounds

Reactions of organolithium compounds

Reactions with carbon acids

Reactions with alkylating agents

Reactions with carbonyl compounds

Organomagnesium compounds

Preparation of organomagnesium compounds

Reactions of organomagnesium compounds

Formation of carbon-carbon bonds

Formation of carbon-hydrogen bonds

Formation of carbon-heteroatom bonds

Formation of carbon-nitrogen bonds

Formation of carbon-phosphorus bonds

Formation of carbon-oxygen bonds

Formation of carbon-sulfur bonds

Formation of carbon-halogen bonds

Organozinc compounds

Preparation of organozinc compounds

Reactions of organozinc compounds

Reactions with carbonyl compounds

Reactions with alkenes

Transition metal-based organometallic compounds

Organocopper compounds

Preparation of organocuprate reagents

Reactions of organocuprate reagents

Reactions with alkylating agents

Reactions with carbonyl compounds

Reactions with α,β-unsaturated carbonyl compounds

Copper-Catalyzed reactions

Palladium-catalyzed reactions

Pd(II) and Pd(0)

Pd(II)-catalyzed reactions

Pd(II)-catalyzed reaction of alkenes

Pd(II)-catalyzed reaction of alkynes

Pd(II)-catalyzed reaction of arenes

Pd(0)-catalyzed reactions

The Heck reaction

The Tsuji-Trost reaction

Carbonylation reactions

The cross-coupling reactions

The Negishi cross-coupling

The Stille cross-coupling

The Suzuki cross-coupling

The Sonogashira cross-coupling

The reaction of aryl halides (or pseudo halides) with non-organometallic nucleophiles

Organoboranes

Substitution of the C-B bond with a C-O bond

Substitution of the C-B bond with a C-N bond

Substitution of the C-B bond with a C-halogen bond

Substitution of the C-B bond with a C-C bond

Substitution of the C-B bond with a C-H bond

 

POLYMER CHEMISTRY AND ENVIRONMENTALLY DEGRADABLE POLYMERS

General structure of polymers.

Basic definitions

Molecular weights and molecular weight distributions

Regioisomery and stereoregularity

Primary, secondary, and tertiary structure

Crystalline and amorphous polymers

Synthesis of polymers

Step-wise polymerization

Crosslinking by step-wise polymerization

Chain polymerization

Radical polymerization

Ionic polymerization

Cationic polymerization

Anionic polymerization

Co-ordination polymerization

Ring opening polymerization

Environmentally degradable polymers

Environmental problems related to the use of plastics

Definition of biodegradability and compostability

Environmentally degradable polymers

Production of plastics from renewable sources

Biodegradable oxidizable polymers

 

ORGANIC SPECTROSCOPY

Nuclear Magnetic Resonance

The Resonance Phenomenon

Chemical Shift

Chemical Equivalence and Signal Intensity

A Simple 1H-NMR Spectrum

Coupling Constant

Dependence of the Proton Coupling Constant on the Molecular Structure

More Complex Spectra

A Real Life 1H-NMR Spectrum

2D Homonuclear Spectra

13C Spectra

2D Heteronuclear Spectra

Mass Spectrometry

Brief Outline of the Technique

Common Ionization Techniques

Sensitivity and Resolution

Ion analysis

Mass Spectrum

Isotope Content

Fragmentation pattern

 

Isotope effects, Isotope separation and isotope fractionation

Isotope Effects

Mechanical Effects

Isotope Effects in Spectroscopy

Isotope Effects in Chemical Equilibria

Isotope Exchange Equilibria

Isotope Effects on Phase Equilibria

Vapor Pressure Isotope Effects

Isotope Effects on other Phase Equilibria

Isotope Effects on some Physicochemical Properties

Kinetic Isotope Effects

Classification and Determination of Kinetic Isotope Effects

Theory of Kinetic Isotope Effects

Mass-independent Isotope Effects

Biochemical and Biological Isotope Effects

Physiological Effects of Heavy Water

Isotope Fractionation in Biological Processes

Isotope Separation

Isotope Separation Processes

Isotopic Fractionation in Nature

Variations in the Isotope Ratio of some Light Elements in Nature

Hydrogen

Carbon

Oxygen

Stable Isotopes in Food and Drink Authentication

 

Radiometric Dating and Tracing

Major concerns

Limitations

Radioactive decay

Chemical separation techniques

Mass spectrometry

Thermal ionization mass spectrometry (TIMS)

Inductively coupled plasma mass spectrometry (ICP-MS)

Secondary ion mass spectrometry (SIMS)

Sensitive high resolution ion microprobe (SHRIMP)

Accelerator mass spectrometry (AMS)

Gas-source mass spectrometry

Methods and applications

Rb-Sr and Sm-Nd

Evolution of the crust-mantle system

Past human and animal migration

K-Ar, Ar-Ar

U-Pb

Lu-Hf

Re-Os

Thermochronometry

Cosmogenic nuclides

Sediment recycling

Geomorphological processes

Paleo-erosion rates

Disequilibrium dating

U-Th disequilibrium in young volcanic rocks

U-Th disequilibrium in carbonates

Extinct radionuclides

Radiation-damage dating methods

Fission-track dating

The luminescence method

 

Radiochemical techniques

Characterization of the radioactive targets and sources 

Separation techniques of radioactive elements  

Activity measurements 

Main aspects in sample preparation for activity measurements

Useful sample-mounting techniques

Choice of counting conditions

Methods for determining absolute decay rates

Decontamination 

Measuring the extent of contamination-decontamination

An overview of the experimental decontamination techniques

Physical decontamination methods

Chemical decontamination

Electrochemical decontamination

Other decontamination techniques

Selection criteria for the decontamination method

Contamination, decontamination in nuclear power plants

Sources and significance of the radioactive contamination at nuclear reactors

Radioactive contamination-decontamination: general consideration

Decontamination technologies used in nuclear power plants

Surface chemical effects of chemical decontamination technologies  a case study

 

Radionuclides in CHEMICAL RESEARCH

Neutron Activation Analysis

Radiotracers

The Tracer Principle

Selection of Radioactive Tracers

Preparation and Acquisition of Radiotracers

Application of Radiotracers

Determination of the Mass of Mercury in Mercury Cathode Tanks

Determination of Distribution Ratio

Solubility

Reaction rates and Mechanisms

Surface and Phase Boundary Reactions

Diffusion

Isotope Dilution Analysis

Volume of Water in the Human Body

Radioimmunoassay

Radiometric Titrations

Positron Emission Tomography (PET)

Miscellaneous Industrial Applications

Gamma Spectroscopy

Basic Principles of Gamma Spectroscopy

The Natural Line Width

Other Modes for De-excitation

The Spectrometer

Detectors

The Electronics

Practical Aspects of Gamma Spectroscopy

Energy Calibration of the Spectrometer

Identification of Nuclides

Efficiency

Resolution

Compton Background

Applications

X-ray Fluorescence Analysis

Principles

The Primary Source of Radiation

Spectrometers

Wavelength-dispersive Spectrometers

Energy-dispersive Spectrometers

Detectors

Total Reflection Geometry

XRF in Practice

Calibration and Identification of X-ray Lines

Attenuation of X-rays

Matrix Effects

Standards

Applications

 

RADIATION BIOLOGY AND RADIATION PROTECTION

Dosimetry

Radiation Types

Ionizing Radiation

Nonionizing Radiation

Effects of Ionizing Radiation on Molecules, Cells, Tissues and Organs of Living Systems

Dose Quantities and Units

Absorbed Dose (symbol: D)

Equivalent Dose (symbol: HT)

Effective Dose (symbol: E)

Exposure Dose (symbol: X)

External and Internal Dose

Individual and Collective Doses (symbol: S)

Determination of Dose

Dose and Dose Rate Meters

ICRU Sphere Phantom

Detectors

Radiation Biology

Effects on Cells

Health Effects of Radiation Exposures

Stochastic Effects

Deterministic Effects

Irradiation in Pregnancy

Radiation Sickness and Tissue Sensitivities

Low Dose Dilemma

Effects of Factors Modifying the Radiation Response

Genomic Instability

Bystander Effect

Adaptive Response

Gene Regulation

Biological Dosimetry

Lymphocyte Metaphase Chromosomes

Fluorescent in situ Hybridization (FISH) Technique

Lymphocyte Micronuclei

Premature Chromosome Condensation (PCC)

Radiation Protection

Objectives of Protection

International Institutes Involved in Regulatory Aspects

Principles of Protection

Reference Levels

Dose Limits

Dose Constraint

Changes in Dose Limitation

Optimization and the ALARA Principle

Infrastructure of Radiation Protection

Practice

Exemption

Intervention and Action

Factors to Reduce Exposure from External Sources

Categories of Exposures

Occupational Radiation Protection

Personnel Monitoring

Film Badge

Thermoluminescent Dosimeter

Radon Dosimeter

Personal Portable Dosimeter

Pocket Dosimeter

Whole Body Counter

Exposure of Workers

Caution Signs

Hand-Foot Contamination Monitor

Monitoring at Workplaces

Transportation of Radioactive Material

Medical Radiation Protection

Medical X-ray Imaging

Nuclear Medicine

Radiotherapy

Release of Patients Administered a Radiopharmaceutical

Guidance Level of Medical Exposure

Environmental Radiation Protection

Natural Sources

Artificial Sources

Risk Assessment

 

RADIATION CHEMISTRY

Absorption of radiation energy 

Energy absorption

Formation and decay of ion pairs

Radiation sources, dosimeters 

Radiation sources

Dosimetric quantities

Dosimeters

Techniques in radiation chemistry, pulsed radiolysis  

Steady-state techniques

Pulse radiolysis

Radiation chemistry of some classes of compounds

Water and aqueous solutions

Radiolysis mechanism

Reactions of intermediates

Water as reactor coolant

Gases

Oxygen and nitrogen-oxygen mixtures

Methane

Inorganic solids

Ice

Metals, semiconductors

Organic materials

Alkanes, alkenes and aromatic hydrocarbons

Other organic molecules

Polymerization and irradiation of polymers

Polymerization kinetics

Polymer decomposition

Biopolymers

DNA and its constituents

Polysaccharides

Amino acids, peptides

Lipids

Radiation technology 

Characteristics of radiation technologies

Synthesis

Industrial radiation technologies

Flue gas treatment

Food irradiation

Sterilization

Drinking and wastewater treatment

Hot atom chemistry 

 

Radiochemistry and Radiopharmaceutical Chemistry FOR MEDICINE

Production of Medical Radionuclides 

Productions Using Nuclear Reactors

Neutron Radiative Capture

Neutron Capture Followed by Particle Emission

Neutron-induced Fission

Yield

Examples

Productions Using Cyclotrons

Types of Cyclotrons

Targetry

Cyclotron-produced Positron Emitters for PET Imaging

Cyclotron-produced Photon Emitters for SPECT Imaging

Cyclotron-produced Therapeutic Radionuclides

Productions Using Radionuclide Generator System

Equations of Radioactive Decay and Growth

Generator-produced Positron Emitters for PET

Generator-produced Photon Emitters for SPECT

Generator-produced Particle Emitters for ERT

In vivo Generators

Radiopharmaceutical Chemistry for Non-invasive Molecular Imaging 

Carbon-11 Labeled Molecules

Synthetic Pathways of 11C-labeling

11C-compounds for Drug Development

11C-radiopharmaceuticals for PET Imaging

Fluorine-18 Labeled Molecules

Synthetic Pathways of 18F-labeling

Application of 18F-compounds

Technetium-99m Labeled Molecules

Synthetic Pathways of 99mTc-labeling

Application of 99mTc-compounds

Radiopharmaceutical Chemistry for Endoradiotherapy

Therapeutic Radionuclides

β--particle Emitting Radionuclides

α-particle Emitting Radionuclides

Low-energy Electron Emitters

Examples of Radiotherapeutics

Microspheres, Particles, Radiocolloids

Me3+ Ligand Complexes

Peptides and Proteins Labeled via Bifunctional Chelating Agents

 

CHEMISTRY OF THE ACTINIDE ELEMENTS

Sources of Actinide Elements

Natural Sources

Artificial Production of Actinides

Electronic Structure and Oxidation States 

Electronic Structure of Actinide Atoms and Ions

Oxidation States

The Metallic State

Preparation of Actinide Metals

Crystal Structures and Properties

Electronic Structures

Superconductivity

Actinide Compounds

Oxides (Stoichiometric and Non-Stoichiometric)

Other Inorganic Compounds

Crystal Structures and Ionic Radii

Coordination Complexes and Coordination Compounds

Organoactinide Compounds

Actinide chemistry in solution  

Stable and Unstable Ions in Aqueous Solution

Reduction Potentials

Hydrolysis and Polymerization

Ion Exchange Chromatography

Other Separations Technologies

Environmental Actinide Chemistry 

Actinide Elements of Natural Origin

Artificial Actinides

Actinides in the Hydrosphere

Actinide Sorption and Mobility

Hazards

Biological Behavior of Actinides 

General Considerations

State of Actinide Elements in Body Fluids

Uptake of Actinide Elements in the Liver

Uptake of Actinides by Bone

Bioremediation of Actinides from the Environment

Toxicology  

Ingestion and Inhalation

Acute Toxicity of Plutonium

Long-Term Effects of Ingested Plutonium

Removal of Actinide Elements from the Body

 

PRODUCTION AND CHEMISTRY OF TRANSACTINIDE ELEMENTS

Brief History of Discovery 

Production and Nuclear Decay Studies of Transactinides

Heavy-ion Fusion Reaction

Production and Identification of Transactinide

Production of Transactinides with 48Ca Ions

Nuclear Structure of the Heaviest Nuclei

Chemical Properties of Transactinides Element 

Atom-at-a-Time Chemistry

Relativistic Effects in Heavy Element Chemistry

Atomic Properties

Experimental Techniques

Production of Transactinides Nuclides

State of the Art in Experiments of Transactinides Chemistry

Experimental Studies of Chemical Properties

Element 104, Rutherfordium (Rf)

Element 105, Dubnium (Db)

Element 106, Seaborgium (Sg)

Element 107, Bohrium (Bh)

Element 108, Hassium (Hs)

Elements 109, Meitnerium (Mt), through Element 112

Future Prospects 

 

NUCLEAR WASTE MANAGEMENT AND THE NUCLEAR FUEL CYCLE

Classification of Radioactive Wastes

High-level Waste (HLW)

Intermediate-level Waste (ILW)

Low-level Waste (LLW)

Who is Responsible for Radioactive Wastes? 

Pertinent Legislation in the US Regarding Radioactive Wastes: An Example

Splitting the Atom for Energy 

Status of Nuclear Power World-wide  

Commercial Nuclear Power Generation

Nature of HLW as a Function of Time 

Fast Reactors 

The Nuclear Fuel Cycle  

Options in the Fuel Cycle that Impact Waste Management

Once-Through Fuel Option

The Reprocessing Fuel Cycle (RFC)

Advanced Fuel Cycle (AFC)

Important Characteristics of Actinides

Separations Technologies for the Nuclear Fuel Cycle  

PUREX Process

DIAMEX Process

TRUEX Process

TRAMEX Process

TALSPEAK Process

Stereospecific Extractants

Non-aqueous Processes

Volatility Processes

Molten Salt Processes

Electrochemical Separations using Non-Aqueous Processes

Advanced Fuel Cycle Concepts and Partitioning and Transmutation (P&T)

Transmutation of Minor Actinides

Transmutation of the Long-lived Fission Products

Partitioning Schemes for the Minor Actinides and Long-lived Fission Products

Aqueous Chemical Processing 

Improved PUREX Process -Removal of Np, I, and Tc

UREX and UREX+ Processes

Non-Aqueous Chemical Processing

Transmutation Devices for the Advanced Fuel Cycle 

Strategies for Implementation of an Advanced Fuel Cycle

Generation IV Nuclear Energy Systems   

Advanced Fuel Cycle Development to Support Generation IV Energy Systems

The Advanced Fuel Cycle Initiative (AFCI)

Areas of Scientific Concerns in the AFCI

Future of P&T 

 

HIGH -INTENSITY LASERS IN NUCLEAR SCIENCE

Laser induced Photo-Reactions and Photo-Fission 

Laser induced heavy ion fusion

Sample preparation   

Laser generation of protons and neutrons   

Laser generation of positrons  

 

NUCLEAR FORENSICS

General Approach

Analytical Methodology

Classical Forensic Investigations

Nuclear Forensic Investigations

Radiometric Methods

Mass Spectrometric Methods

Microstructural Techniques

Specific Developments

Data Interpretation

Reference Data

Reactor Type Determination (Pu Production)

Geolocation

International Cooperation

 

NUCLEAR PROCESSES IN NATURE

Terrestrial Nuclear Processes

Geoneutrinos

The Oklo Phenomenon

Living on Radioactivity

Celestial Nuclear processes

The Gamma-sky

Gamma-ray Bursts

Gamma Rays from Cosmic Nuclei

Nuclear Fingerprints of a Near-Earth Supernova

Heavy-element Nucleosynthesis

Neutron Capture Reactions

Gamma Induced Reactions

 

Subatomic Particles, Nuclear Structure and Stability

Particles and Forces - the Standard Model in a Nutshell

The Origin of Nuclear Force

Classification of Particles and Forces

The Color Charge

Characterization of the Atomic Nucleus

Nuclear Radius and Mass Density

Nuclear Spin, Electric and Magnetic Properties of Nuclei

The One-nucleon Shell Model of the Nucleus

Systematics of Stable Elements, Nuclides and Nuclei

Mass and Energy

Criterion for Spontaneity: Q-value and Mass Excess -Application for Beta and Alpha decay

The Average Binding Energy Per Nucleon

The Weizsäcker Formula -Liquid-drop Explanation for SF

Towards Greater Stability - Radioactive Decay

Radioactive Decay and the Chart of Nuclides

Decay Modes Revisited

More on Gamma Decay

More on Spontaneous Fission

Exotic and Rare Decay Modes

 

THE WORLD OF CHEMISTRY

Centrality of Chemistry in Human Activities, Life, and Culture

The Impact of Chemistry on Technological Development

Peculiarities of Chemical Processes

Relevance of the Molecular Approach

Molecular Dynamics

Engineering of Industrial Processes

Polymeric Materials

Advanced Materials, Nanostructures, and Molecular Electronics

 

A HISTORY OF CHEMISTRY

The Birth of Chemistry as a Science

From Alchemy to Chemistry

The Skeptical Chemist

Pneumatic Chemistry

The Chemical Revolution

Definition of the Building Blocks of Chemistry

Atoms

Molecules

The Elements

Discovery of the Elements

The Periodic Law of the Elements

Thermodynamics

The Laws of Thermodynamics

The Development of Thermochemistry

Chemical Affinity

Chemical Dynamics

Reaction Kinetics

Catalysis

The States of Matter

The Gaseous State

The Liquid State

The Solid State

Valence Theory

Spectroscopic Analysis

Spectral Analysis

Color Analysis

X-ray Diffraction Analysis

Stereochemistry

Electrochemistry

Organic Chemistry

From Vital Forces to Synthesis

Importance of Accurate Quantitative Analysis

Problem of the Representation of Organic Molecules

New Synthetic Routes

Discoveries of New Products and Less Expensive Processes

Synthetic Dyes

Explosives

Plastics and Fibers

The Alkali Industry

Nitrogen Fixation

Oxidation of SO2

Evolution of the Cracking of Petroleum

Tetraethyl Lead

 

CHEMICAL MATTER: ELEMENTS AND THEIR CLASSIFICATION THROUGH THE PERIODIC SYSTEM

The Building Up of the Periodic Table

The Periodical Trends of Some Physical Properties

Ionization Energies

Size of Atoms

Electron Affinities

Some Periodical Trends of the Chemical Behavior

From Metals to Nonmetals

The Binding Energies

Electronegativity

The Electrochemical Properties of the Metallic Elements

 

THE CONTRIBUTION OF NOBEL LAUREATES TO CHEMISTRY

The Discovery of New Elements

The Filling and Expansion of the Periodic Table

The Isotopes

The Properties of Atoms

The Birth of Nuclear Chemistry

The Development of Quantum Mechanics

The Properties of Molecules

The Discovery of Coordination and Metallorganic Compounds

The Discovery of New Organic Molecules

The Emergence of Quantum Chemistry

The Expansion of Thermodynamics

Equilibrium Thermodynamics

Nonequilibrium Thermodynamics

The Dynamics of Chemical Reactions

Kinetics of Heterogeneous and Homogeneous Processes

The Identification of the Activated State

New Synthetic Routes for Useful Products

Via Catalysis

Via Synthesis in Extreme Experimental Conditions

Natural Products via Multistep Synthesis

Via New Synthetic Strategies

Via New Reactants or Reagents

The Understanding of Natural Processes

From Ferments to Enzymes

Understanding the Mechanism of Action of Enzymes

Mechanisms of Important Natural Processes

Characterization of Biologically Important Molecules

The Development of DNA-Based Chemistry

The Identification of Chemical Entities

Analytical Methods

New Separation Techniques

The Development of New Instrumentation for Structure Analysis

 

CHEMICAL LABORATORY TECHNIQUES

Common Laboratory Apparatus

Glassware

Heating of the Reaction Mixture

Burners

Heating Baths

Electric Hot Plates and Electric Heating Mantles

Cooling of the Reaction Mixtures

Stirring

The Reaction

Batch Reactors

Continuous Stirred-Tank Reactors

Tubular Reactors

Pulse Reactors

Isolation and Purification Techniques

Filtration

Extraction

Liquid-Liquid Extraction

Liquid-Solid Extraction

Crystallization

Distillation

Theoretical Aspects

Simple Distillation

Fractional Distillation

Distillation under Reduced Pressure

Steam Distillation

 

GAS AND LIQUID CHROMATOGRAPHY

Evolution and Classification of Chromatography

Adsorption Chromatography

Partition Chromatography

Ion-Exchange and Size-Exclusion Chromatography

Affinity Chromatography

Chromatographic Theory

Distribution of Analytes Between Phases

Separation Efficiency

Gas Ch