Evidence for conformational differences in aqueous and crystalline structures of α-bungarotoxin and cobratoxin

Laser Raman spectroscopy has been employed to investigate the structures of α-bungarotoxin (Bungarus multicinctus) and cobratoxin (Naja naja siamensis) in H₂O and D₂O solutions. Structures of the aqueous neurotoxins are compared with one another and with the X-ray crystal structures. The results indicate that the solution and crystal molecular structures of cobratoxin are in substantial agreement with one another, but those of α-bungarotoxin are not. Raman data provide no evidence for strained disulfides in aqueous α-bungarotoxin, although strained CSSC dihedral angles are indicated for the X-ray crystal structure. The data are interpreted as evidence for a strained molecular conformation of α-bungarotoxin in the crystal, which converts to a relaxed, more energetically favorable conformation in aqueous solution. Raman spectra also suggest more β-strand secondary structure in aqueous α-bungarotoxin (47 ± 5%) than in the crystalline form ( < 10%). The high β-strand content measured by Raman spectroscopy could be due to either a secondary structure in solution that is appreciably different than that of the crystal, or to the imprecision of the Raman method in distinguishing peptide configurations that are vibrationally equivalent but conformationally inequivalent. Aqueous α-bungarotoxin and cobratoxin also differ from one another in amino acid side chain orientations and interactions, though not in main chain conformations. Different geometries are indicated for cystine CCSS dihedral angles, and different hydrogen bonding states are indicated for internal tyrosines. Tyrosine-24 of α-bungarotoxin is shown to donate a strong hydrogen bond to a negative acceptor, deduced to be glutamate-41, whereas the equivalently positioned residue of cobratoxin is apparently hydrogen bonded to solvent molecules.     

A Convenient Halogenation Procedure for the Preparation of α-Halocarbonyl Compounds

Except for substituted acetophenones (p-Y-C₆H₄COCH₃, Y=H, Br, CH₃O), simple ketones, β-ketoesters and 1,3-diketones reacted smoothly with a preformed homogeneous mixture of hydrochloric acid and potassium permanganate in acetonitrile to give moderate to good yields of the corresponding α-chlorocarbonyl compounds. Mixtures of α-chloro- and α,α-dichlorocarbonyl compounds were obtained for substituted acetophenones. Brominations proceeded similarly with higher yields when the hydrochloric acid was replaced with hydrobromic acid.     

Preparation,characterization and properties of β-chitin and N-acetylated β-chitin

Free amino groups in β-chitin from squid pen were acetylated to obtain N-acetylated β-chitin. After careful control of degree of acetylation, thermal and mechanical properties of β-chitin and N-acetylated β-chitin were compared. The structural differences of β-chitin and N-acetylated β-chitin were characterized by Fourier transform infrared (FTIR) and wide-angle x-ray diffraction (WAXD) analysis. The results indicated that the crystallinity of N-acetylated β-chitin was higher than that of β-chitin and N-acetylated β-chitin exhibited characteristics similar to α-chitin. Equilibrium water content (EWC) of β-chitin reached to about 50% and this hydrophilic nature was assumed to be caused by a relatively weak hydrogen bonding force of β-chitin with parallel main chains. On the other hand, EWC of N-acetylated β-chitin was 40% due to the introduction of ordered structure. β-chitin and N-acetylated β-chitin have the tensile strength of 0.4 and 0.7 Mpa in the swollen state, respectively. Viscoelastic properties and thermal relaxation behaviors were investigated by dynamic mechanical thermal analysis (DMTA). DMTA spectra of these samples showed that α-transition peaks of β-chitin and N-acetylated β-chitin were observed at 170 and 190°C, respectively. These relaxation peak maxima were assigned to be their glass transition temperature. In addition, a second relaxation peak of β-chitin resulting from acetamide groups was found at 112°C and a broad relaxation peak of N-acetylated β-chitin at around 81–100°C. As a result of thermogravimetric analysis, 10% weight loss temperatures of β-chitin and N-acetylated β-chitin were 270 and 285°C, respectively. © 1996 John Wiley & Sons, Inc.     

Evidence of dynamic heterogeneity as obtained from dielectric and brillouin light-scattering studies of poly(n-hexylmethacrylate)

We report dielectric relaxation and Rayleigh-Brillouin spectroscopic measurements on the side chain polymer poly(n-hexylmethacrylate), PHMA (T_g = 268 K), exhibiting a broad glass transition region. The dielectric loss curves can be represented by single Havriliak-Negami functions in the temperature range of 260–450 K. The width of the distribution relaxation function is a decreasing function of temperature up to T = 333 K ≊ 1.24 × T_g and remains virtually constant above that temperature. This is interpreted as marking the merging of the α-process with a slow β-relaxation in agreement with the value of the cooperativity length associated with the α-mode. Hence above that temperature, the relaxation times confirm well to an Arrhenius temperature dependence. The hypersonic dispersion deduced from the Brillouin spectra (210–550 K) surprisingly peaks at temperatures near T_g which bears no relation to the main α-relaxation. This structural relaxation is rather associated with the side hexyl group motion showing striking resemblance with the hypersonic dispersion in molecular liquids. It is conceivable that the observed damping in PHMA is dynamically related to the internal plasticization effect of the hexyl group. © 1996 John Wiley & Sons, Inc.     

The Constituents of the Leaves of Chamaecyparis Formosensis Matsum

Forty one terpenoidal compounds were isolated from the essential oil of Chamaecyparis formosensis Matsum. The dominant component is α-pinene. Other major components include β-pinene, 3-carene, α-terpineol, γ-muurolene, and kaurene.     

A Mild Isomerization Reaction for β,γ‐Unsaturated Ketone to α,β‐Unsaturated Ketone

A series of β,γ‐unsaturated ketones were isomerized to their corresponding α,β‐unsaturated ketones by the introduction of DABCO in iPrOH at room temperature. The endo‐cyclic double bond (β,γ‐position) on ketone was rearranged to exo‐cyclic double bond (α,β‐position) under the reaction conditions.     

Einkristallstudien zur Temperaturabhängigkeit der Kristallstruktur von α-Na3Hg

Temperature Dependent Single Crystal Investigations of α-Na₃Hg In contrast to β-Na₃Hg (rhomboedrally distorted Li₃Bi-type) α-Na₃Hg crystallizes in a hitherto poorly understood variant of the Na₃As-type. Based on temperature dependent measurements of poly- and single crystalline samples (?100°C < T < +35°C) we show, that in particular the sodium atoms (Na1) located in the region of the octahedral Hg₆-holes show a pronounced temperature dependent dynamical behaviour. To a lesser extend this is also true for the tetrahedrally coordinated Na-atoms (Na2). With increasing temperature the former ones more and more approach the centers of the opposite triangular faces of mercury atoms, limiting the Hg₆-octahedra along [001]. Occupation of the latter positions by sodium atoms would lead to unusual short interatomic distances d_{Na? Hg}. However before reaching this unreasonable situation α-Na₃Hg decomposes under formation of β-Na₃Hg.     

A Novel Method for the Synthesis of α,β‐Unsaturated Amides Mediated by Samarium Diiodide

Promoted by Samarium diiodide (SmI₂), α,β‐unsaturated amides were formed from nitrogen anions (formed in situ by the reduction of nitro compounds) and α,β‐unsaturated esters. This reaction contrasts with the conjugate addition between amines and α,β‐unsaturated esters promoted by samarium triiodide (SmI₃) and provides an alternative attractive way to obtain α,β‐unsaturated amides using SmI₂.     

Catalyst-Controlled Regiodivergent Synthesis of α/β-Dipeptide Derivatives via N-Allylic Alkylation of O-Alkyl Hydroxamates with MBH Carbonates

A controllable and regiodivergent N-allylation reaction involving readily available O-alkyl hydroxamates derived from natural α-amino acids has been developed, allowing regiospecific access to α/β-dipeptides containing α-unsaturated β-amino acids moieties in moderate to good yields. The regioselectivity could be conveniently switched by alternation of the catalysts and solvents.     

Zwei neue Phosphorsulfide

Two New Phosphorus Sulfides Jason [1] prepared by the reaction of triphenylantimony sulfide with α-P₄S₅ and α-P₄S₇ new phosphorus sulfides. The application of this method on α-P₄S₄ yielded the main product γ-P₄S₅ which was assumed to appear in low concentration in phosphorus-sulfur melts by Bjorholm and Jakobsen [2]. In addition the new isomers δ-P₄S₆ and ϵ-P₄S₆ were identified by ³¹P-NMR spectroscopy. Furtheron the sulfurization of α-P₄S₅ and β-P₄S₅ was studied. Reaction paths are suggested. In all cases the primary reaction is an exocyclic addition of phosphorus, followed by insertion or further addition.     

Oxidation-Induced Structural Alterations and Its Effect on Chaperone Function of Rat Lens α-Crystallin

An ascorbate-FeCl₃-EDTA-H₂O₂ system was used to oxidize rat lens α-crystallins. Under this oxidative insult, the chaperone activity of α-crystallin toward γ-crystallin was shown to decrease significantly, which is quite different from the result reported by Wang and Spector. (Invest. Ophthalmol. Vis. Sci. 1995 , 36, 311-321.) Fluorescence spectroscopy and circular dichroism were employed to characterize the structural changes of oxidized α-crystallin. It was found that fluorescence intensity of l-anilinonaphthalene-8-sul-phonate (ANS) bound to oxidized α-crystallin increased comparing to that bound to normal α-crystallin, suggesting oxidation causes the exposure of more hydrophobic regions. Further, α-crystallin's fluorescence intensity in response to tryptophan residues showed a pseudo first order decline. Amino acid analysis of normal versus oxidized α-crystallin confirmed actual decline in tryptophan levels, showing about 80% of tryptophan being modified after 10-hour oxidation. Circular dichroism showed both changes in the secondary and tertiary structures of oxidized α-crystallin, characterized by a large loss of aromatic-type amino acid interactions and a large loss of β-sheet structure. In conclusion, modified tryptophan, secondary and tertiary structural changes of α-crystallin correlate best with the reduction of chaperone function, the curves all showing a linear slope for 10 hours, then plateauing. These results indicate that the decrease of α-crystallin chaperone activity is attributed to the structural changes.     

Chain Multiplication of Fatty Acids to Precise Telechelic Polyethylene

Starting from common monounsaturated fatty acids, a strategy is revealed that provides ultra‐long aliphatic α,ω‐difunctional building blocks by a sequence of two scalable catalytic steps that virtually double the chain length of the starting materials. The central double bond of the α,ω‐dicarboxylic fatty acid self‐metathesis products is shifted selectively to the statistically much‐disfavored α,β‐position in a catalytic dynamic isomerizing crystallization approach. “Chain doubling” by a subsequent catalytic olefin metathesis step, which overcomes the low reactivity of this substrates by using waste internal olefins as recyclable co‐reagents, yields ultra‐long‐chain α,ω‐difunctional building blocks of a precise chain length, as demonstrated up to a C₄₈ chain. The unique nature of these structures is reflected by unrivaled melting points (T _m=120 °C) of aliphatic polyesters generated from these telechelic monomers, and by their self‐assembly to polyethylene‐like single crystals.     

Lateral thermal expansion of chitin crystals

Measurements of the thermal expansion coefficients (TECs) of chitin crystals in the lateral direction are reported. We investigated highly crystalline α chitin from the Paralithodes tendon and an anhydrous form of β chitin from a Lamellibrachia tube from room temperature to 250 °C, using X‐ray diffraction at selected temperatures in the heating process. For α chitin, the TECs of the a and b axes were α_a = 6.0 × 10⁻⁵ °C⁻¹ and α_b = 5.7 × 10⁻⁵ °C⁻¹, indicating an isotropic thermal expansion in the lateral direction. However, the anhydrous β chitin exhibited an anisotropic thermal expansion in the lateral direction. The TEC of the a axis was constant at α_a = 4.0 × 10⁻⁵ °C⁻¹, but the TEC of the b axis increased linearly from room temperature to 250 °C, with α_b = 3.0–14.6 × 10⁻⁵ °C⁻¹. These differences in the lateral thermal expansion behaviors of the α chitin and the anhydrous β chitin are due to their different intermolecular hydrogen bonding systems. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 168–174, 2001     

Stereoselective reduction of α-substituted β-keto esters by hydrostannane/organotin triflate

Stereoselective reduction of α-substituted β-keto esters is achieved by the combined use of hydrostannane/organotin triflate. syn-Aldols are obtained with more than 90% selectivities.     

A convenient synthesis of α,α′‐ homo‐ and α,α′‐hetero‐bifunctionalized poly(ε‐caprolactone)s by ring opening polymerization: The potentially valuable precursors for miktoarm star copolymers

Two new ring opening polymerization (ROP) initiators, namely, (3‐allyl‐2‐(allyloxy)phenyl)methanol and (3‐allyl‐2‐(prop‐2‐yn‐1‐yloxy)phenyl)methanol each containing two reactive functionalities viz. allyl, allyloxy and allyl, propargyloxy, respectively, were synthesized from 3‐allylsalicyaldehyde as a starting material. Well defined α‐allyl, α′‐allyloxy and α‐allyl, α′‐propargyloxy bifunctionalized poly(ε‐caprolactone)s with molecular weights in the range 4200–9500 and 3600–10,900 g/mol and molecular weight distributions in the range 1.16–1.18 and 1.15–1.16, respectively, were synthesized by ROP of ε‐caprolactone employing these initiators. The presence of α‐allyl, α′‐allyloxy and α‐allyl, α′‐propargyloxy functionalities on poly(ε‐caprolactone)s was confirmed by FT‐IR, ¹H, ¹³C NMR spectroscopy, and MALDI‐TOF analysis. The kinetic study of ROP of ε‐caprolactone with both the initiators revealed the pseudo first order kinetics with respect to ε‐caprolactone consumption and controlled behavior of polymerization reactions. The usefulness of α‐allyl, α′‐allyloxy functionalities on poly(ε‐caprolactone) was demonstrated by performing the thiol‐ene reaction with poly(ethylene glycol) thiol to obtain (mPEG)₂‐PCL miktoarm star copolymer. α‐Allyl, α′‐propargyloxy functionalities on poly(ε‐caprolactone) were utilized in orthogonal reactions i.e copper catalyzed alkyne‐azide click (CuAAC) with azido functionalized poly(N‐isopropylacrylamide) followed by thiol‐ene reaction with poly(ethylene glycol) thiol to synthesize PCL‐PNIPAAm‐mPEG miktoarm star terpolymer. The preliminary characterization of A₂B and ABC miktoarm star copolymers was carried out by ¹H NMR spectroscopy and gel permeation chromatography (GPC). © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 844–860     

Synthesis of Taiwan Cobra Venom Cardiotoxin II Synthesis of Protected Hexapeptide,Sequence 44-49 and Protected Tripeptide,Sequence 50-52

The protected hexapeptide (sequence 44-49) and the protected tripeptide (sequence 50-52) of Taiwan Cobra (Naja naja atra) venom cardiotoxin were synthesized by stepwise coupling and fragment coupling methods. The protected hexapeptide is Nps-Lys(Z)-Ser-Ser-Leu-VaI-Leu-OMe and the protected tripeptides are Nps-Lys(Z)-Tyr(Bzl)-Val-OMe and Boc-Lys(Z)-Tyr(Bzl)-VaI-OMe.     

Triphenylphosphine‐Mediated Reduction of Electron‐Deficient Propargyl Ethers to the Allylic Ethers

Semihydrogenation of α,β‐unsaturated ynoates and ‐ynones bearing a γ‐alkoxy group can be performed using triphenylphosphine and water. α,β‐Unsaturated ynoates were reduced to a mixture of cis and trans α,β‐unsaturated enoates, whereas, ynones were reduced to trans α,β‐unsaturated enones as the only products.     

Mass spectroscopy and SEC of SRM 1487, a low molecular weight poly(methyl methacrylate) standard

Matrix Assisted Laser Desorption Ionization (MALDI) Time of Flight (TOF) Mass Spectrometry (MS) was used to study the molecular weight distribution (MWD) and the number of α-methyl styrene (α-MeSty) repeat units in SRM 1487, a narrow MWD poly(methyl methacrylate) (PMMA) standard reference material of about 6300 g/mol, which was initiated with α-MeSty. It was found that each PMMA polymer chain had from zero to seven α-MeStys per chain. The MWD of the polymer chains containing a fixed number of α-MeStys was obtained. The MWD, M_w, and the average number of α-MeSty at a given molecular weight from MALDI TOF MS compare well with those obtained from more traditional methods such as ultracentrifugation and Size Exclusion Chromatography (SEC). The implications of the number of α-MeStys per chain is discussed in terms of the chemistry of anionic polymerization. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 2409–2419, 1997     

Shape‐Selective Alkylation of Naphthalene over Zeolites: Steric Interaction of Reagents with Zeolites

Steric interaction of reagents with zeolites was studied in isopropylation, sec‐butylation, and tert‐butylation of naphthalene (NP) over several large‐pore zeolites to elucidate the mechanism of selective catalysis. Selectivities for dialkylnaphthalene (DAN) isomers were influenced by the type of zeolite and bulkiness of alkylating agent. Selective formation of β,β‐ and 2,6‐diisopropylnaphthalene (DIPN) occurred only over H‐mordenite (MOR) in the isopropylation of NP using propene; bulky transition states of α,α‐ and α,β‐DIPN are excluded because of steric restriction by the channels, resulting in selective formation of β,β‐ and 2,6‐DIPN. However, low selectivities for β,β‐ and 2,6‐DIPN were observed over the zeolites, SSZ‐24 (AFI), SSZ‐55 (ATS), and SSZ‐42 (IFR) with 12‐membered‐ring (12‐MR) pore entrances of one‐dimensional channels, CIT‐5 (CFI), UTD‐1 (DON), and SSZ‐53 (SFH) with 14‐membered‐ring (14‐MR) pore entrances of one‐dimensional channels, and Y‐zeolite (FAU), zeolite β (BEA), and CIT‐1 (CON) with 12‐MR pore entrances of three‐dimensional channels, because their channels are too large for the exclusion of bulky isomers. Catalysis over these zeolites occurs under kinetic and/or thermodynamic control, resulting in predominant formation of α,α‐ and α,β‐DIPN at lower temperatures and an increase of the stable isomer β,β‐DIPN at higher temperatures. The selectivities for β,β‐ and 2,6‐DAN were enhanced with the increase in bulkiness of alkylating agents: 1‐butene for sec‐butylation and 2‐methylpropene for tert‐butylation. In particular, β,β‐di‐tert‐butylnaphthalene (DTBN) was selectively formed in the tert‐butylation. The selectivities for β,β‐ and 2,6‐DAN were enhanced even in large channels: the transition states of the least bulky isomers only fit the channels because other bulky isomers are excluded by steric restriction of the channels. However, tert‐butylation over FAU, BEA, and CON had selectivities for 2,6‐DTBN of around 50–60%, although selectivities for β,β‐DTBN were almost 100% selectivity; these zeolites can hardly recognize the differences between 2,6‐ and 2,7‐DTBN. The results indicate that the fitting of the least bulky isomers to zeolite channels, leading to the exclusion of other bulky isomers, is essential for highly shape‐selective catalysis.     

Theoretical Study Of β2,3‐Peptide Models

Conformational features of α,β‐disubstituted β^2,3‐dipeptide models have been studied with quantum mechanics method. Geometries were optimized with the HF/6‐31G** method, and energies were evaluated with the B3LYP/6‐31G** method. Solvent effect was evaluated with the SCIPCM method. For (2S,3S)‐β^2,3‐dipeptide model 1 , a six‐membered‐ring hydrogen bonded structure is most stable. However, the conformation corresponding to the formation of the 14‐helix is only about 1.7 kcal/mol less stable in methanol solution, indicating that the 14‐helix is favored if a (2S,3S)‐β^2,3‐polypeptide contains more than 5 residues. On the other hand, the conformation corresponding to the formation of β‐sheet is most stable for (2R,3S)‐β^2,3‐dipeptide model 2 , suggesting that this type of β‐peptides is intrinsically favored for the formation of β‐sheet secondary structure.