Interface structure and formation mechanism of diffusion-bonded joints of TiAl-based alloy to titanium alloy

Vacuum diffusion bonding of a TiAl based alloy (TAD) to a titanium alloy (TC2) was carried out at 1 273 K for 15～120 min under a pressure of 25 MPa . The kinds of the reaction products and the interface structures of the joints were investigated by SEM, EPMA and XRD. Based on this, a formation mechanism of the interface structure was elucidated. Experimental and analytical results show that two reaction layers have formed during the diffusion bonding of TAD to TC2. One is Al rich α(Ti)layer adjacent to TC2,and the other is (Ti 3Al+TiAl)layer adjacent to TAD,thus the interface structure of the TAD/TC2 joints is TAD/(Ti 3Al+TiAl)/α(Ti)/TC2.This interface structure forms according to a three stage mechanism,namely(a)the occurrence of a single phase α(Ti)layer;(b)the occurrence of a duplex phase(Ti 3Al+TiAl)layer;and(c)the growth of the α(Ti)and (Ti 3Al+TiAl)layers.

Die sinter bonding in air using copper formate preform for formation of full-density bondline

Pressure-assisted sinter bonding was performed in air at 250−350℃ using a preform comprising copper formate particles to form a bondline that is sustainable at high temperatures.H2 and CO generated concurrently by the pyrolysis of copper formate at 210℃ during the sinter bonding removed the native oxide and other oxides grown on bulk Cu finishes,enabling interface bonding.Moreover,Cu produced in situ by the reduction of Cu(II)accelerated the sinter bonding.Consequently,the bonding achieved at 300−350℃ under 5 MPa exhibited sufficient shear strength of 20.0−31.5 MPa after 180−300 min of sinter bonding.In addition,an increase in pressure to 10 MPa resulted in shear strength of 21.9 MPa after an extremely short time of 30 s at 250℃,and a near-full-density bondline was achieved after 300 s.The obtained results indicate the promising potential of the preform comprising copper formate particles for high-speed sinter bonding.

Double network self-healing hydrogel based on hydrophobic association and ionic bond for formation plugging

Self-healing hydrogels have attracted tremendous attention in the field of oil and gas drilling and production engineering because of their excellent self-healing performance after physical damage.In this study,a series of double network self-healing(DN_(SA))hydrogels based on hydrophobic association and ionic bond were prepared for plugging pores and fractures in formations in oil and gas drilling and production engineering.The mechanical,rheological,and self-healing properties of the DN_(SA)hydrogels were investigated.Results revealed that the DN_(SA)hydrogels exhibited excellent mechanical properties with a tensile stress of 0.67 MPa and toughness of 7069 kJ/cm^(3) owing to the synergistic effect of the double network.In addition,the DN_(SA)hydrogels exhibited excellent compression resistance,notch insensitivity,and self-healing properties.The DN_(SA)-2 hydrogel was granulated and made into gel particles with different particle sizes and used as a plugging agent.The self-healing mechanism of DN_(SA)-2 hydrogel particles in fractures was explored,and it’s plugging effect on fractures of different widths and porous media of different permeabilities were investigated.Experimental results revealed that the plugging capacity of the DN_(SA)-2 hydrogel particles for a fracture with width of 5 mm and a porous medium with a permeability of 30μm^(2) was 3.45 and 4.21 MPa,respectively,which is significantly higher than those of commonly used plugging agents in the oilfield.The DN_(SA)hydrogels with excellent mechanical and self-healing properties prepared in this study will provide a new approach for applying hydrogels in oil and gas drilling and production engineering.

O-O bond formation mechanisms during the oxygen evolution reaction over synthetic molecular catalysts

Water oxidation is one of the most important reactions in natural and artificial energy conversion schemes.In nature,solar energy is converted to chemical energy via water oxidation at the oxygen-evolving center of photosystem II to generate dioxygen,protons,and electrons.In artificial energy schemes,water oxidation is one of the half reactions of water splitting,which is an appealing strategy for energy conversion via photocatalytic,electrocatalytic,or photoelectrocatalytic processes.Because it is thermodynamically unfavorable and kinetically slow,water oxidation is the bottleneck for achieving large-scale water splitting.Thus,developing highly efficient water oxidation catalysts has attracted the interests of researchers in the past decades.The formation of O-O bonds is typically the rate-determining step of the water oxidation catalytic cycle.Therefore,better understanding this key step is critical for the rational design of more efficient catalysts.This review focuses on elucidating the evolution of metal-oxygen species during transition metal-catalyzed water oxidation,and more importantly,on discussing the feasible O-O bond formation mechanisms during the oxygen evolution reaction over synthetic molecular catalysts.

Tuning the O–O bond formation pathways of molecular water oxidation catalysts on electrode surfaces via second coordination sphere engineering

A molecular [Ru(bda)]-type(bda = 2,2’-bipyridine-6,6’-dicarboxylate) water oxidation catalyst with 4-vinylpyridine as the axial ligand(Complex 1) was immobilized or co-immobilized with 1-(trifluoromethyl)-4-vinylbenzene(3 F) or styrene(St) blocking units on the surface of glassy carbon(GC) electrodes by electrochemical polymerization, in order to prepare the corresponding poly-1@GC, poly-1+P3 F@GC, and poly-1+PSt@GC functional electrodes. Kinetic measurements of the electrode surface reaction revealed that [Ru(bda)] triggers the O–O bond formation via(1) the radical coupling interaction between the two metallo-oxyl radicals(I2 M) in the homo-coupling polymer(poly-1), and(2) the water nucleophilic attack(WNA) pathway in poly-1+P3 F and poly-1+PSt copolymers. The comparison of the three electrodes revealed that the second coordination sphere of the water oxidation catalysts plays vital roles in stabilizing their reaction intermediates, tuning the O–O bond formation pathways and improving the water oxidation reaction kinetics without changing the first coordination structures.

Switching O-O bond formation mechanism between WNA and I2M pathways by modifying the Ru-bda backbone ligands of water-oxidation catalysts

Understanding the seven coordination and O-O coupling pathway of the distinguished Ru-bda catalysts is essential for the development of next generation efficient water-oxidation catalysts based on earthabundant metals.This work reports the synthesis,characterization and catalytic properties of a monomeric ruthenium catalyst Ru-bnda(H2 bnda=2,2’-bi(nicotinic acid)-6,6’-dicarboxylic acid)featuring steric hindrance and enhanced hydrophilicity on the backbone.Combining experimental evidence with systematic density functional theory calculations on the Ru-bnda and related catalysts Ru-bda(H_(2)bda=2,2’-bipyridine-6,6’-dicarboxylic acid),Ru-pda(H_(2)pda=1,10-phenanthroline-2,9-dicarboxylic acid),and Ru-biqa(H_(2)biqa=(1,1’-biisoquinoline)-3,3’-dicarboxylic acid),we emphasized that seven coordination clearly determines presence of Ru^(Ⅴ)=O with high spin density on the ORu^(Ⅴ)=O atom,i.e.oxo with radical properties,which is one of the necessary conditions for reacting through the O-O coupling pathway.However,an additional factor to make the condition sufficient is the favorable intermolecular faceto-face interaction for the generation of the pre-reactive[Ru^(Ⅴ)=O…O=Ru^(Ⅴ)],which may be significantly influenced by the secondary coordination environments.This work provides a new understanding of the structure-activity relationship of water-oxidation catalysts and their potential to adopt I2M pathway for O-O bond formation.

Necessity of structural rearrangements for O-O bond formation between O5 and W2 in photosystemⅡ

Numerous aspects of the water oxidation mechanism in photosystemⅡhave not been fully elucidated,especially the O-O bond formation pathway.However,a body of experimental evidences have identified the O5 and W2 ligands of the oxygen-evolving complex as the highly probable substrate candidates.In this work,we studied O-O bond formation between O5 and W2 based on the native Mn4 Ca cluster by density functional calculations.Structural rearrangements before the formation of the S_(4) state were found as a prerequisite for O-O bond formation between O5 and W2,regardless if the suggested pathways involving the typical Mnl(Ⅳ)-O·species or the recently proposed Mn4(Ⅶ)(O)2 species.Possible alternatives for the S2→S_(3) and S_(3)→S_(4) transitions accounting for such required rearrangements are discussed.These findings reflect that the structural flexibility of the Mn4 Ca cluster is essential to allow structural rearrangements during the catalytic cycle.

Effect of Wetting and NiAl_2O_4 Spinel Formation on the Bonding between Al_2O_3 and Ni

Al2O3-Ni interface formed under vacuum condition is non-wetting and weak. Severe instantaneous intedecial reaction (i.e. wetting) at the Al2O3-Ni interface promoted by oxygen can create a strengthened interface. The NiAl2O4 spinel-Ni intedece is weak and growth of the spinel interphase is detrimental to the Al2O3-Ni intedecial bonding. A proper control of the oxygen partial pressure can achieve wetting while avoiding the existence of spinel at the interface, producing stronger interfaces by both mechanical interlocking and more intimate chemical bonding in an Al2O3-20 vol pct Ni composite.

A^1HNMR STUDY ON THE FORMATION AND BREAKING OF INTRAMOLECULAR HYDROGEN BONDS OF BILIRUBIN IN CDCl_3-DMSO-d_6 BINARY SOLVENT

The formation and breaking of intramolecular hydrogen bonds of bilirubin in CDCl_3-DMSO-d_6 binary solvent have been investigated by means of NMR spectroscopy.The chemical shifts of protons at dipyrrinone lactam C=O and N-H,Pyrrole N-H,C-5,C-15 and methylene groups of 8,12-propionic acid side-chains changed markedly as a function of composition of the binary solvent.The hydrogen bond formation is dependent on the conformation of propionic acid side-chains.

Formation Sites and Microscopic Conformation Study on the Konjac Glucomannan Molecular Helices

In this work, the formation sites, helical parameters and hydrogen bond positions of Konjac glucomannan molecular helices were investigated using molecular dynamic simulation method. To our interest, the KGM chain is mainly composed by local left and right helix struetttres. The formation sites of KGM chain might locate at the chain-segments containing acetyl groups, and the left helix is the favorable conformation of KGM. Temperature-dependent molecule conformation study indicates that the right helix is dominant when the temperature is lower than 343 K, above which, however, the left helix is dominating （right helix disappears）. In addition, intramolecular hydrogen bonds in the left helix can be found at the -OH groups on C（2）, C（4） and C（6） of mannose residues; comparably, the intramolecular hydrogen bonds in the right helix can be mainly observed at the -OH groups on C（4） and C（6） of the mannose residues and C（3） of the glucose residues. In conclusion, molecular dynamic simulation is an efficient method for the microscopic conformation study of glucomannan molecular helices.

Resultant gradient information, kinetic energy and molecular virial theorem

Resultant gradient-information is introduced and applied to problems in chemical reactivity theory. This local measure of the structural information contained in (complex) wavefunctions of electronic states is related to the system overall kinetic energy combining the modulus (probability) and phase (current) contributions. The grand-ensemble representation of thermodynamic equilibria in open systems demonstrates the physical equivalence of the variational energetic and information principles. It is used and to relate the populational derivatives of ensemble-average functionals in both these representations, which represent reactivity criteria for diagnosing the charge-transfer (CT) phenomena. Their equivalence is demonstrated by using the in situ potential and hardness descriptors to predict the direction and optimum amount of CT. The virial theorem is generalized into thermodynamic quantities and used to extract the kinetic energy component from qualitative energy profiles in the bond-formation and (exo/endo)-ergic reactions. The role of electronic kinetic energy in such chemical processes is reexamined, the virial theorem implications for the Hammond postulate of reactivity theory are explored, and variations of the structural-information in chemical processes are addressed. The maximum thermodynamic information rule is formulated and "production" of the gradient-information in chemical reactions is addressed. The Hammond postulate is shown to be indexed by the geometric derivative of resultant gradient-information at transition-state complex.

Transfer of disulfide bond formation modules via yeast artificial chromosomes promotes the expression of heterologous proteins in Kluyveromyces marxianus

Kluyveromyces marxianus is a food-safe yeast with great potential for producing heterologous proteins.Improving the yield in K.marxianus remains a challenge and incorporating large-scale functional modules poses a technical obstacle in engineering.To address these issues,linear and circular yeast artificial chromosomes of K.marxianus(KmYACs)were constructed and loaded with disulfide bond formation modules from Pichia pastoris or K.marxianus.These modules contained up to seven genes with a maximum size of 15 kb.KmYACs carried telomeres either from K.marxianus or Tetrahymena.KmYACs were transferred successfully into K.marxianus and stably propagated without affecting the normal growth of the host,regardless of the type of telomeres and configurations of KmYACs.KmYACs increased the overall expression levels of disulfide bond formation genes and significantly enhanced the yield of various heterologous proteins.In high-density fermentation,the use of KmYACs resulted in a glucoamylase yield of 16.8 g/l,the highest reported level to date in K.marxianus.Transcriptomic and metabolomic analysis of cells containing KmYACs suggested increased flavin adenine dinucleotide biosynthesis,enhanced flux entering the tricarboxylic acid cycle,and a preferred demand for lysine and arginine as features of cells overexpressing heterologous proteins.Consistently,supplementing lysine or arginine further improved the yield.Therefore,KmYAC provides a powerful platform for manipulating large modules with enormous potential for industrial applications and fundamental research.Transferring the disulfide bond formation module via YACs proves to be an efficient strategy for improving the yield of heterologous proteins,and this strategy may be applied to optimize other microbial cell factories.

Synthesis of nucleoside-peptide conjugate with disulfide bond as linker at C-5 of uridine

In order to prepare pyrimidine nucleoside-peptide conjugate concisely, we developed a one-pot synthetic strategy. Started from uridine, 5-S-acetyl-thiomethyl-2＇,3 ＇-di-O-isopropylidene-uridine （4） was synthesized as the key intermediate in four steps. Under acidic condition, compound 4 was deprotected and reacted with PySS-R （8, 12, 15, Py = 2-pyridyl, R = amino acid or peptide） in one pot to form uridine conjugates （9, 13, 2） with disulfide bond as linker.

Ion source effect on the bond length of ^4HeH^＋

The bond length of ^4HeH^＋ resulting from collision-induced destruction is measured at 1.4420 MeV using the Coulomb Explosion Technique. The measured bond length of ^4HeH^＋ is 0.094±0.003nm. The bond length of ^4HeH^＋ obtained with our radio frequency （RF） ion source is larger than that obtained with a duoplasmatron ion source at Argonne National Laboratory （ANL）, but the bond lengths of H^＋2 and H^＋3obtained separately by ANL and by us with the two different ion sources are consistent with each other, which implies that there exists an ion source effect on the bond length of ^4HeH^＋. The main reason why the 4^4HeH^＋ bond lengths obtained by the two different ion sources are different is also discussed.

Vacuum diffusion bonding of Ti_(2)AlNb alloy and TC4 alloy

The Ti_(2)AlNb alloy was joined with TC4 alloy by vacuum diffusion bonding.The relationship between bonding parameters,and joint microstructure and shear strength was investigated.The results indicated that the diffusion of Al,Ti,Nb and V elements across bonding interface led to the formation of three reaction layers:B2/βlayer andα2 layer on the TC4 side,andα2+B2/βlayer on the Ti_(2)AlNb side.The bonding temperature determined the atomic activity,thus controlling the growth of reaction layers and influencing the shear strength of the joint.When the Ti_(2)AlNb alloy and TC4 alloy were bonded at 950℃for 30 min under 10 MPa,the shear strength of the joint reached the maximum of 467 MPa.The analysis on the fracture morphology showed that the fracture occurred within the B2/βlayer and the fracture model was ductile rupture.Meanwhile,the formation mechanism of the Ti_(2)AlNb/TC4 joint was discussed in depth.

A Modified Method for the Synthesis of Tetradentate Ligand Involving Peptide Bond

In view of the importance of picolinic acid (Pa) in preventing cell growth and arresting cell cycle, attempts were made to design, synthesize and characterize two new Pa based tetradentate ligands (DPPTR and DPPTY) with a modified procedure. The procedure reported here avoids by-products and provides better yield and purity.

New Generation Semi-Automatic Thermosonic Wire Bonder

The physical and technological aspects of wire ball-wedge bonding in the assembly of integrated circuits are considered.The video camera and the pattern recognition system(PRS)of new bonder helps to provide accurate positioning of the bonding tool on the chip pads of integrated circuits.The formation of the loop wire cycle is ensured by the synchronous movement of the bonding head along the Z axis and the working table along the XY axes based on the servo drive.A feature of the bonder is that it can bond all the wire loops of the electronic device according to the pre-recorded program without needing to align the bonding points.

Recent Advances of Modern Protocol for C-C Bonds—The Suzuki Cross-Coupling

Over the past 20 years, small molecule solid phase synthesis has become a powerful tool in the discovery of novel molecular materials. In the development of organic chemistry, the carbon-carbon bond formation has always been one of the most useful and fundamental reaction. The current review summarizes recent developments in metal-catalyzed coupling reactions. The following method is discussed in detail—the cross-coupling of aryl halides with aryl boronic acids (the Suzuki coupling), and the others C-C bond formation reactions as the palladium-catalyzed reaction between an aryl and (or) alkyl halide and a vinyl functionality (the Heck reaction);and the palladium-catalyzed cross-coupling reaction of organostannyl reagents with a variety of organic electrophiles (the Stille reaction)—are mentioned.

ATR-FTIR Analysis on Aliphatic Hydrocarbon Bond(C-H)For­mation and Carboxyl Content during the Ageing of DC Air Plasma Treated Cotton Cellulose and Its Impact on Hydrophilicity

The surface of the cotton fabric was modified using a direct current(DC)air plasma treatment and hence enhances its hydrophilicity.The Box-Behnken approach(design expert software)was used to optimise the input process parameters.The sample prepared under optimized condition is subjected to ATR-FTIR and Field Emission Scanning Electron Microscopy(FESEM)studies in order to determine the changes in hydrogen bond energies(EH),Total Crystallinity Index(TCI),Hydrogen Bond Intensity(HBI),Lateral Order Index(LOI),functionalization,lattice parameters(a,b,c&β),degree of crystallinity(in%)and surface etching.The ageing of this sample has been studied by comparing the values of carboxyl content and AC-C/AC-O-C ratio calculated using data extracted from ATR-FTIR spectra of the sample recorded periodically for one month.

Visible light-mediated C—P bond formation reactions

Organophosphorus compounds have attracted continuous attention in materials science, agrochemical and pharmaceutical fields due to their unique bioactivities. Thus, the development of novel and robust manners for the construction new C—P bond has therefore gained great interests in synthetic organic chemistry. Because of their intrinsic sustainability and green chemistry character, visible light-induced photoredox catalysis has been widely applied in the construction of new chemical bonds, including the formation of C—P bond. In this review, we summarized recent achievements in C—P bond formation reactions initiated by visible light-induced photoredox catalysis, which mainly focusing on the discussion of reaction design and the mechanism.